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Two compositionally complex oxides (CCOs) of the type (Hf0.2Zr0.2Ce0.2Gd0.2 RE0.2)O2-δ, were synthesized via self-propagating room temperature synthesis where RE=Yb for one of the two, while in the other case, Yb was replaced by equal concentrations of Pr and Nd. Heat-treatment at varied temperatures between 900 °C – 1500 °C and phase evolution studies revealed the formation of a single phase with a FCC structure with the Yb containing oxide. However, the substitution of Yb with Pr and Nd resulted in an additional secondary FCC phase. Furthermore, Raman spectroscopy confirmed pyrochlore-type ordering in both compounds with exemplification of superlattice planes in high-resolution transmission electron microscopic images. The presence of 3+ and 4+ cations confirmed by X-ray photoelectron spectroscopy, is in accordance with the results on the pyrochlore structure containing two different cationic species.

High-entropy rare-earth (RE) zirconates with pyrochlore structure were successfully fabricated by pressureless and spark plasma sintering. RE2Zr2O7 compound with nominal composition (La0.2Y0.2Gd0.2Nd0.2Sm0.2)Zr2O7 was prepared by simple glycine nitrate procedure (GNP). GNP process yielded powders with low crystallinity and after subsequent calcination, well crystalline ceramics were formed. During calcination defective fluorite (F-RE2Zr2O7) and crystal pyrochlore (Py-RE2Zr2O7) structures coexist. Formation of pure crystalline pyrochlore occurs after sintering at 1450 °C. High-density ceramics, free of any additives, were obtained after powders compaction and pressureless (PS), as well as field assisted sintering technique (FAST) at 1450 °C. Theoretical investigations of the high-entropy RE2Zr2O7 pyrochlore systems were performed. Unit cell parameter of the obtained Py-RE2Zr2O7 is 10.5892(2) Å and 10.5999(2) Å for PS and FAST sintering, respectively, which is in good agreement with the results of Density Functional Theory (DFT) calculations. The thermal diffusivity of sintered samples at room temperature was ∼0.7 mm2/s for both sintering methods. Resumen: Se fabricaron con éxito, mediante sinterización por plasma sin presión y por chispa, los circonatos de tierras raras (RE) de alta entropía con estructura de pirocloro. El compuesto RE2Zr2O7 con composición nominal (La0,2Y0,2Gd0,2Nd0,2Sm0,2)Zr2O7 se preparó mediante un procedimiento simple de nitrato de glicina (GNP). El proceso GNP produjo polvos con baja cristalinidad y después de la posterior calcinación, se formaron cerámicas bien cristalinas. Durante la calcinación coexisten estructuras defectuosas de fluorita (F-RE2Zr2O7) y pirocloro cristalino (Py-RE2Zr2O7). La formación de pirocloro cristalino puro se produce después de la sinterización a 1.450 °C. Después de la compactación de polvos y sin presión (PS), así como por la técnica de sinterización asistida en campo (FAST) a 1.450 oC, se obtuvieron cerámicas de alta densidad, libres de aditivos. Se realizaron investigaciones teóricas de los sistemas de pirocloro RE2Zr2O7 de alta entropía. El parámetro de celda unitaria del Py-RE2Zr2O7 obtenido es 105.892(2) Å y 105.999(2) Å para la sinterización PS y FAST, respectivamente, lo que está de acuerdo con los resultados de los cálculos de la teoría funcional de la densidad (DFT). La difusividad térmica de las muestras sinterizadas a temperatura ambiente fue de ∼ 0,7 mm2/s para ambos métodos de sinterización.

Hafnium carbide (HfC) is a refractory compound known for its exceptional mechanical, thermal, and electrical properties. This compound has gained significant attention in materials science and engineering due to its high melting point, extreme hardness, and excellent thermal stability. This study presents crystal structure prediction via energy landscape explorations of pristine hafnium carbide supplemented by data mining. Apart from the well-known equilibrium rock salt phase, we predict eight new polymorphs of HfC. The predicted HfC phases appear in the energy landscape with known structure types such as the WC type, NiAs type, 5-5 type, sphalerite (ZnS) type, TlI type, and CsCl type; in addition, we predict two new structure types denoted as ortho_HfC and HfC_polytype, respectively. Moreover, we have investigated the structural characteristics and mechanical properties of hafnium carbide at the DFT level of computation, which opens diverse applications in various technological domains.

Studying the interaction of inorganic systems with organic ones is a highly important avenue for finding new drugs and treatment methods. Tumor cells show an increased demand for amino acids due to their rapid proliferation; thus, targeting their metabolism is becoming a potential oncological therapeutic strategy. One of the inorganic materials that show antitumor properties is titanium dioxide, while its doping was found to enhance interactions with biological systems. Thus, in this study, we investigated the energy landscape of glutamine (L), an amino acid, on pristine and doped TiO2 surfaces. We first locally optimized 2D-slab structures of pristine and Au/Ag/Cu-doped anatase (001 and 101 surfaces) and similarly optimized a single molecule of glutamine in vacuum. Next, we placed the pre-optimized glutamine molecule in various orientations and on a variety of locations onto the relaxed substrate surfaces (in vacuum) and performed ab initio relaxations of the molecule on the substrate slabs. We employed the DFT method with a GGA-PBE functional implemented in the Quantum Espresso code. Comparisons of the optimized conformations and electronic structures of the amino acid in vacuum and on the surfaces yield useful insights into various biological processes.

Oxynitrides of cerium are expected to have many useful properties but have not been synthesized so far. We identified possible modifications of a not-yet-synthesized Ce3O3N compound, combining global search (GS) and data mining (DM) methods. Employing empirical potentials, structure candidates were obtained via global optimization on the energy landscape of Ce3O3N for different pressure values. Furthermore, additional feasible structure candidates were found using data mining of the ICSD database. The most promising structure candidates obtained were locally optimized at the ab initio level, and their E(V) curves were computed. The structure lowest in total energy, Ce3O3N-DM1, was found via local optimization starting from a data mining candidate and should be thermodynamically metastable up to high pressures.

In the last decade, an immense progress has been made in white LEDs, mainly due to the development of red-emitting phosphors. In this paper, we report on the synthesis of Eu3+ activated Y2MoO6 by a self-initiated and self-sustained method. The obtained powder was calcined at various temperatures in the 600–1400 °C range and examined by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and photoluminescence spectroscopy (PL). The results revealed that all powders are single phase Y2MoO6:Eu3+, with particle size in the nanorange at lower treatment temperatures (600 and 800 °C) and in the microrange at higher calcination temperatures (1000–1400 °C). The obtained powders are promising materials for white light-emitting diodes as they can efficiently absorb energy in 324–425 nm region (near-UV to blue light region) and emit at 611 nm in the red region of the spectrum, while exhibiting high thermal and chemical stability.

A Density Functional Theory (DFT) study has been performed in order to investigate behaviour of barium sulfide (BaS) at high pressures, and relationship between computed properties, in great detail. Novel predicted and previously synthesized BaS modifications have been calculated using Local Density Approximations (LDA) and Generalized Gradient Approximation (GGA) functionals. In particular, a detailed investigation of structural changes and its corresponding volume effect up to 100 GPa, with gradual pressure increase, has been performed from the first principles. Band gap engineering of the experimentally observed BaS phases at high pressures has been simulated and structure-property relationship is investigated. For each of the predicted and experimentally observed BaS structures, elastic constants and mechanical properties under compression have been investigated (e.g. ductility/brittleness, hardness, anisotropy). This study offers a new perspective of barium sulphide as a high pressure material with application in ceramics, optical and electrical technologies.

Potential non-toxic pink and red ceramic pigments based on CeO2 were successfully synthesized by self-propagating room temperature method and thermally treated at 600, 900 and 1200 °C for 15 min. The structure, morphology and optical properties, as well as thermal stability of Ce1-xErxO2-δ and Ce1-xPrxO2-δ (x = 0.05) were examined. Single-phase composition of all obtained CeO2 pigments was confirmed using XRPD method and Raman spectroscopy and it was not dependent on temperature. The mechanism of structural behaviour was thoroughly examined using Raman and FTIR spectroscopy. Nanometric dimensions of the crystallites of all pigments were confirmed using XRPD, TEM and FE-SEM analysis. Colour properties were dependent on the temperature treatment, and their position in the chromaticity diagram was studied using UV/VIS spectrophotometry. Colour efficiency measurements were supplemented by colorimetric analysis. It is proved that all samples are thermally stable in the investigated temperature range (up to 1200 °C), and their potential application as environmentally friendly pigments of desired colour is confirmed.

The paper presents results of the influence of mechanical activation of shungite, a carbon-mineral rock material rich in silica and carbon, on its sintering behaviour, and obtaining of pure SiC ceramics. The mechanical activation of the starting powder was performed in a high-energy ball mill in time intervals from 30 to 480 min. The phase composition of the starting powders and sintered samples was analysed by the X-ray diffraction method. The first traces of SiC were detected after sintering at 1350 °C for 2 h in an Ar atmosphere, along with traces of unreacted SiO2. The scanning electron microscopy was performed in order to determine changes in the microstructure. Sintering was performed at various temperatures for 2 h, in an Ar atmosphere and a vacuum. Dielectric properties of the sintered samples were measured in the frequency range from 1 to 500 MHz. The obtained results indicate that the sintered powder is a good candidate for applications as an absorber of electromagnetic waves in microwave engineering.

We report on a new class of ZnO/ZnS nanomaterials based on the wurtzite/sphalerite architecture with improved electronic properties. Semiconducting properties of pristine ZnO and ZnS compounds and mixed ZnO1−xSx nanomaterials have been investigated using ab initio methods. In particular, we present the results of our theoretical investigation on the electronic structure of the ZnO1−xSx (x = 0.20, 0.25, 0.33, 0.50, 0.60, 0.66, and 0.75) nanocrystalline polytypes (2H, 3C, 4H, 5H, 6H, 8H, 9R, 12R, and 15R) calculated using hybrid PBE0 and HSE06 functionals. The main observations are the possibility of alternative polytypic nanomaterials, the effects of structural features of such polytypic nanostructures on semiconducting properties of ZnO/ZnS nanomaterials, the ability to tune the band gap as a function of sulfur content, as well as the influence of the location of sulfur layers in the structure that can dramatically affect electronic properties. Our study opens new fields of ZnO/ZnS band gap engineering on a multi-scale level with possible applications in photovoltaics, light-emitting diodes, laser diodes, heterojunction solar cells, infrared detectors, thermoelectrics, or/and nanostructured ceramics.

Nanosized Mg-doped ceria powders were obtained by self-propagating room temperature reaction without using surfactants or templates. X-ray diffraction analysis and field emission scanning microscopy results showed that the doped samples are solid solutions with fluorite-type structure and spherical morphology. Raman spectra revealed an increase in the amount of oxygen vacancies with the increase of Mg concentration. This increasing results in a narrowing of the bandgap of CeO2. The photocatalytic performances of the Mg-doped ceria solid solutions were evaluated by decomposing an organic dye, crystal violet under UV irradiation. The Mg-doped ceria solid solutions exhibit significantly better photocatalytic activity than the pure CeO2 and commercial TiO2. The higher first rate constant of the Mg-doped samples demonstrated that they are much more efficient than TiO2 and CeO2 under UV light. Mg2+ dopant ions and oxygen vacancies play a significant role in the enhancement of photocatalytic performances of the Mg-doped ceria.

A number of studies have indicated that the implementation of Si in CrN can significantly improve its performance as a protective coating. As has been shown, the Cr-Si-N coating is comprised of two phases, where nanocrystalline CrN is embedded in a Si3N4 amorphous matrix. However, these earlier experimental studies reported only Cr-Si-N in thin films. Here, we present the first investigation of possible bulk Cr-Si-N phases of composition Cr2SiN4. To identify the possible modifications, we performed global explorations of the energy landscape combined with data mining and the Primitive Cell approach for Atom Exchange (PCAE) method. After ab initio structural refinement, several promising low energy structure candidates were confirmed on both the GGA-PBE and the LDA-PZ levels of calculation. Global optimization yielded six energetically favorable structures and five modifications possible to be observed in extreme conditions. Data mining based searches produced nine candidates selected as the most relevant ones, with one of them representing the global minimum in the Cr2SiN4. Additionally, employing the Primitive Cell approach for Atom Exchange (PCAE) method, we found three more promising candidates in this system, two of which are monoclinic structures, which is in good agreement with results from the closely related Si3N4 system, where some novel monoclinic phases have been predicted in the past.

In this paper, bismuth ferrite (BFO) particles synthesized by controlled hydrothermal process, where the particles of small sizes and with high purity were obtained. Structural analysis showed that non-annealed powder can be perfectly fitted to rhombohedral space group R3c and contains a very small amount of secondary phase, whereas the final product (annealed at 800 °C) represents single-phase perovskite powder with high crystallinity. HRTEM analysis confirmed existence of twin stacking faults, which are responsible for enhanced magnetic properties. EPR measurements suggested existence of electrons trapped by vacancies or defects. It has been proposed that existence of Fe3+−OV defect complex could be generated at elevated temperatures followed by formation of trivalent Fe ions, which intensely provide local 3d moments.

The investigation of nano-mechanical properties of sphene sintered under ultra-high pressures in the order of 4 GPa is done using indentation techniques. An indentation hardness of 6.6 GPa and reduced elastic modulus of 112.3 GPa is reported at maximum load of 7 mN. The material exhibits a high elastic recovery (∼59.1%) and the nature of deformation mechanism has been comprehended from the plastic work ratio. In addition, the fracture toughness of the material is also evaluated using indentation crack length method.

Nanoemulsion technique, based on Ouzo effect, was applied for synthesis of the pure and silver doped (2.5 and 5 mol%) calcium hydroxyapatite (HAp). After calcination at 500 °C fully crystallized powders were obtained. X-ray powder diffraction analysis accompanied with Rietveld refinement revealed that the synthesized powders were single-phase hydroxyapatite. Raman spectroscopy also confirmed that the synthesized powders were single-phase. The obtained HAp particles were spherical in shape and their sizes were in the nanometer range which was revealed by field emission scanning electron microscopy analysis (FESEM). The successful synthesis of the single-phase Ag doped HAp showed that nanoemulsion method is a simple technique for obtaining pure and doped hydroxyapatite nanospheres.

Spider silk poses excellent mechanical properties, tenacity and elasticity and it has been used as a template for calcite mineralization to improve load bearing strength of osteoconductive calcite. The samples were obtained by mimicking biomineralization for five days in order to follow formation and growth of calcite on the surface of spider silk. Crystal phase was detected by XRD and FTIR spectroscopy. Microstructure, crystal size and its morphology were studied by means of FESEM. After two days of processing, pure calcite phase was obtained, and a size of the formed crystals increased with prolongation of biomineralization.

Carbon cryogel/ceria composite, with 10 wt.% of ceria, was synthesized by mixing of ceria and carbon cryogel (CC). The sample was characterized by field emission scanning electron microscopy, nitrogen adsorption and X-ray diffraction. The adsorption of arsenic(III) ions from aqueous solutions on carbon cryogel/ceria nanocomposite was studied as a function of time, solution pH and As(III) ion concentration. The results are correlated with previous investigations of adsorption mechanism of arsenic(III) on carbon cryogel. Adsorption dose experiments showed that the mass of the adsorbent was reduced for 20 times, in comparison with pure CC, for the same amount of adsorbed arsenic(III) ions. BET isotherm was used to interpret the experimental data for modelling liquid phase adsorption.

A new technology based on bio-templating approach was proposed in this paper. Egg-shell membrane (ESM) has been employed as a natural biotemplate. Fibrous oxide ceramics was prepared by wet impregnation of biological template with water solution of cerium nitrate. The template was derived from membranes of fresh chicken eggs. Repeated impregnation, pyrolysis and final calcination in the range of 600 to 1200 °C in air resulted in template burnout and consolidation of the oxide layers. At low temperatures, the obtained products had structure which corresponded to the negative replication of biological templates. Unique bio-morphic CeO2 microstructures with interwoven networks were synthesized and characterized by scanning electron microscope (SEM) and X-ray diffraction (XRD), whereas low-temperature nitrogen adsorption (BET) method was used in order to characterize porous properties.

The fabrication of SiC-HfC ceramic composite via self-propagating high-temperature synthesis and simultaneous consolidation was investigated. Dense composite consisting of alternating layers of SiC and HfC was obtained by spark plasma sintering of stack of SiC cloths covered by electrophoretically deposited HfO2. The deposited HfO2 was converted into HfC during sintering. The obtained ceramics was characterized in terms of microstructure, cavitation resistance and oxidation resistance. It was shown that spark plasma sintering is effective way to preserve fibre-like mikrostructure of SiC. The obtained material showed good erosion resistance. The surface layer of HfC transformed to HfO2 during oxidation of samples and protected SiC from further oxidation.

In this paper a short review of our results on the synthesis of nanosized CeO2, CaMnO3 and BaCeO3 solid solutions are presented. The nanopowders were prepared by two innovative methods: self propagating room temperature synthesis (SPRT) and modified glycine/nitrate procedure (MGNP). Different types of solid solutions with rare earth dopants in concentrations ranging from 0–0.25 mol% were synthesized. The reactions forming solid solutions were studied. In addition, the characteristics of prepared nanopowders, phenomena during sintering and the properties of sintered samples are discussed.

A novel method for synthesis of carbon cryogel/zeolite composites was obtained. Method considers forming of carbon cryogel from the sol-gel polycondenzation of resorcinol and formaldehyde, followed by freeze drying, and subsequent pyrolysis in presence of different amount of zeolite. Characterization of composite materials by nitrogen adsorption shows that samples are micro- and mesoporous and that specific surface area decrease with increasing the amount of zeolite in samples. XRD method confirms amorphous structure of carbon cryogel and crystalline structure of zeolite, i.e. structure of zeolite has not been destroyed by carbonization process. SEM and EDX analyses reveal homogenous distribution of zeolite through out carbon cryogel and corresponding composition.

The possibility of using domestic Mg-silicate (sepiolite, white) as Si source and novolac resin (as carbon source), for synthesis of fine β-SiC powder at relatively low temperatures (1673−1873 K), was demonstrated. Obtained SiC powders consist of fine β-SiC particles and did not retain the fibrous morphology of starting sepiolites. Carbothermal reduction process, which was used in this study, is greatly influenced by catalyst addition (FeCl3, FeSi). In order to obtain pure SiC powders, it is necessary to completely remove all Mg-species, and catalytic influence of Fe is attributed to FeSi important role in reduction of Mg2SiO4 and MgO into Mg(g). Formation of SiC whiskers is observed only in samples with Fe introduced in form of iron-silicide (FeSi).

In this paper, the results of vertical migration of chloride and sulphate anions in soil are presented. The soil was contaminated with NaCl and CuSO4. Anions migration were monitored during one hydrological year (425 days). The first sample was taken after 150 days and afterwards samples were taken every 50 days. Before the profile contamination physical and chemical analyses of soil have been done. The obtained results show that chloride concentration in soil was in the range from 0.67 mg/kg up to 11.92 mg/kg, while sulphate concentration was in the range from 0.65 mg/kg up to 9.79 mg/kg.

The zirconia/silicon carbide (ZrO2 /SiC) and ZrO2 powders are prepared by carbothermal reduction of natural mineral zircon (ZrSiO4). The zircon powder was mixed with activated carbon as a reducing agent and heattreated in a controlled flow atmosphere of Ar. Phase evolution and phase content were followed as a function of temperature (1573–1973 K) and C/ZrSiO4 ratio (C/ZrSiO4 = 1, 4, 5 and 7), by means of ex-situ X-ray diffraction and SEM/EDS analysis. By varying the temperature and C/ZrSiO4 ratio, different powder compositions were obtained (m-ZrO2; m-ZrO2/c-ZrO2; c-ZrO2; c-ZrO2/SiC).

Nanometric size (Ba, Yb) doped ceria powders with fluorite-type structure were obtained by applying selfpropagating room temperature methods. Tailored composition was: Ce0.95−xBa0.05YbxO2−δ with fixed amount of Ba − 0.05 and varying Yb content “x” from 0.05 to 0.2. Powder properties such as crystallite and particle size and lattice parameters have been studied. Röntgen diffraction analyses (XRD) were used to characterize the samples at room temperature. Also, high temperature treatment (up to 1550°C) was used to follow stability of solid solutions. The mean diameters of the nanocrystals are determined from the full width at half maxima (FWHM) of the XRD peaks. It was found that average diameter of crystallites is less than 3 nm. WilliamsonHall plots were used to separate the effect of the size and strain in the nanocrystals.

This paper presents a study of soils structure and composition using up to date technique, such as scanning electronic microscopy, atomic force microscopy, X-ray diffraction, X-ray fluorescence, as well as some other characterization methods. It was shown that soil particles have porous structure and dimensions in the range from several millimeters to several hundreds of nanometers and consist of different minerals such as kaolin, quartz and feldspate.

Tilia wood was transformed by pyrolysis into carbon preform. This porous carbon preform was infiltrated with TEOS (Si(OC2H5)4), as a source of silica. In situ reaction between the silica and the carbon template occurred in the cellular wall at a hight temperature. Depending on the applied atmosphere, non-oxide (SiC) or oxide (SiO2) ceramics were obtained. Scanning electron microscopy (SEM), X-ray diffraction (XRD), infrared (IR) spectroscopy, mercury porosimetry and BET measurements were employed to characterize the phases and crystal structure of biomorphic ceramics. The experimental results showed that the biomorphic cellular morphology of the wood maintained in both the SiC and SiO2 ceramics, wich consisted of β-SiC with trace of α-SiC and SiO2, respectively.