Interactions in ternary bismuth-containing molybdate systems M2MoO4-Bi2(MoO4)3-Zr(MoO4)2 in the subsolidus region

A fundamental problem in materials science consists in establishing a relationship between the chemical composition, structure, and properties of materials. This issue can be solved through the study of multicomponent systems and the directed synthesis of promising compounds. Of practical interest here are active dielectrics that are based on complex oxide compounds, specifically molybdates. Among complex molybdates and tungstates, ternary caged molybdates of the following structural types are of greatest importance: nasicon, perovskite, langbeinite, etc. Due to their widely varying elemental and quantitative compositions, such molybdates are convenient models for structural and chemical design, as well as the establishment of “composition–structure– properties” genetic relationships. Bismuth-containing complex molybdate systems exhibit the formation of phases having ferro-piezoelectric, ionic, and other properties. In this work, the Rb2MoO4–Bi2(MoO4)3–Zr(MoO4)2 ter nary salt system was studied for the first time using the method of intersecting sections in the subsolidus region (450–650 ℃). To this end, quasibinary sections were identified; triangulation was performed. Ternary molybdates Rb5BiZr(MoO4)6 and Rb2BiZr2(MoO4)6,5 were formed in the system using a ceramic technology. These compounds are isostructural to the previously obtained REE molybdates (M5LnZr(MoO4)6) but contain trivalent bismuth instead of rare earth elements. The structure of Rb5BiZr(MoO4)6 was adjusted via the Rietveld refinement technique using the TOPAS 4.2 software package. The ternary molybdate crystallizes in a trigonal system, with the following unit cell parameters of the R`3c space group: a = 10.7756(2) and c = 39.0464(7) Å. According to the studies of thermal properties exhibited by M5BiZr(MoO4)6, these ternary molybdates undergo the first-order phase transition in the temperature range of 450–600 ºC. The IR and Raman spectra of M5BiZr(MoO4)6 reveal the crystallization of ternary molybdates in the R`3c space group. The conducted comparative characterization of M2MoO4–Bi2(MoO4)3–Zr(MoO4)2 phase diagrams suggests that the phase equilibria of these systems depend on the nature of molybdates of monovalent elements.

A-Site Cation Size Effect on Structure and Magnetic Properties of Sm(Eu,Gd)Cr0.2Mn0.2Fe0.2Co0.2Ni0.2O3 High-Entropy Solid Solutions

Three high-entropy Sm(Eu,Gd)Cr0.2Mn0.2Fe0.2Co0.2Ni0.2O3 perovskite solid solutions were synthesized using the usual ceramic technology. The XRD investigation at room temperature established a single-phase perovskite product. The Rietveld refinement with the FullProf computer program in the frame of the orthorhombic Pnma (No 62) space group was realized. Along with a decrease in the V unit cell volume from ~224.33 Å3 for the Sm-based sample down to ~221.52 Å3 for the Gd-based sample, an opposite tendency was observed for the unit cell parameters as the ordinal number of the rare-earth cation increased. The average grain size was in the range of 5–8 μm. Field magnetization was measured up to 30 kOe at 50 K and 300 K. The law of approach to saturation was used to determine the Ms spontaneous magnetization that nonlinearly increased from ~1.89 emu/g (Sm) up to ~17.49 emu/g (Gd) and from ~0.59 emu/g (Sm) up to ~3.16 emu/g (Gd) at 50 K and 300 K, respectively. The Mr residual magnetization and Hc coercive force were also determined, while the SQR loop squareness, k magnetic crystallographic anisotropy coefficient, and Ha anisotropy field were calculated. Temperature magnetization was measured in a field of 30 kOe. ZFC and FC magnetization curves were fixed in a field of 100 Oe. It was discovered that the Tmo magnetic ordering temperature downward-curve decreased from ~137.98 K (Sm) down to ~133.99 K (Gd). The spin glass state with ferromagnetic nanoinclusions for all the samples was observed. The <D> average and Dmax maximum diameter of ferromagnetic nanoinclusions were calculated and they were in the range of 40–50 nm and 160–180 nm, respectively. The mechanism of magnetic state formation is discussed in terms of the effects of the A-site cation size and B-site poly-substitution on the indirect superexchange interactions.

New triple molybdate and tungstate Na5Rb7Sc2(XO4)9 (X = Mo, W)

New compounds of the composition Na5Rb7Sc2(XO4)9 (X = Mo, W) were obtained via the ceramic technology. The sequences of chemical transformations occurring during the formation of these compounds were established, and their primary characterization was performed. Both Na5Rb7Sc2(XO4)9 (X = Mo, W) were found to melt incongruently at 857 K (X = Mo) and 889 K (X = W). They are isostructural to Ag5Rb7Sc2(XO4)9 (X = Mo, W), Na5Cs7Ln2(MoO4)9 (Ln = Tm, Yb, Lu) and crystallize in the trigonal crystal system (sp. gr. R32). The crystal structures were refined with the Rietveld method using the powder X-ray diffraction data. The thermal expansion of Na5Rb7Sc2(WO4)9 was studied by high-temperature powder X-ray diffraction; it was shown that this triple tungstate belongs to high thermal expansion materials.

Ceramic technology of complex shape from ZrO2 by DLP 3D printing

The article presents the results of 3D printing with ceramic suspensions by DLP method using inorganic dyes.

Architectural Glazed Tiles Used in Ancient Chinese Screen Walls (15th–18th Century AD): Ceramic Technology, Decay Process and Conservation

The glazed tile is an important building material used throughout the history of traditional Chinese architecture. Architectural glazed tiles used to decorate the screen walls of ancient China are studied scientifically for the first time. More than 30 glazed tile samples from the screen walls of the 15th to 18th century AD of the Hancheng Confucian Temple and Town God’s Temple in Shaanxi Province were carefully investigated using SEM–EDS and XRD. Microstructure and chemistry indicated the raw materials, the recipes and the technological choices used to produce the paste and glaze of the glazed tile samples studied. The causes for the key degradation processes of these glazed tiles used as building materials in the screen walls have also been discussed. This work has clear implications for the restoration and conservation treatments on these kinds of ancient Chinese building materials.

Influence of the firing temperature on the dielectric properties of ceramics based on barium titanate

The object of the research is the firing temperature of ceramic materials based on barium titanate. In laboratory conditions, barium titanate was synthesized from raw materials of barium carbonate and titanium dioxide using ceramic technology, taking into account the stoichiometric composition of the compound. In order to study the effect of the firing temperature on the properties of the ceramic material, three temperatures were selected: 1270, 1300, and 1350 °C. The physical properties of the samples (imaginary density, water absorption, open porosity) were determined by the method of hydrostatic weighing in water. The samples were saturated with water after their preliminary evacuation. The dielectric characteristics of the obtained materials were measured on an E7-8CLR automated device (Ukraine) at a frequency of 1 kHz. The structural and morphological features of ceramics based on synthesized barium titanate were investigated by direct scanning electron microscopy and X-ray phase analysis. On the basis of the complex of studies carried out, the technological parameters of the production of ceramics were selected. Thus, the duration of grinding at the first and second stages is 10 and 30 minutes; moisture content of the press powder – 8 %; pressing pressure – 20 MPa; temperature of the first firing – 1000 °С; temperature of the second firing – 1350 °C. The regularity of the change in the dielectric constant on the firing temperature of ceramics based on barium titanate was established. The investigated samples, obtained according to the given technological regime, are characterized by the following indicators: dielectric constant – 259.9; open porosity – 0.02 %; water absorption – 0.01 %; imaginary density – 5.45 g/cm3. The resulting material can be used to create composite ceramic materials that protect biological and technical objects from the effects of electromagnetic radiation, and can also be used to create new functional materials for space, aerospace, electronic engineering and medicine.

Thermal expansion of solid solutions of the Pb(Zr,Ti)O3 system near lead zirconate

Ferroelectric ceramic materials based on the Pb(Zr,Ti)O3 (PZT) system were obtained by two-stage solid-phase synthesis followed by sintering using conventional ceramic technology. On the basis of the studies correlations between the thermal expansion and structural parameters of the investigated solid solutions were established. It was concluded that the obtained data are recommended to be used in the development of devices based on solid solutions with the participation of the PZT system.

Synthesis and properties of double gadolinium tellurites

For the first time, double gadolinium tellurites of the composition GdMIITeO4.5 (MII — Sr, Ba) were synthesized by the solid-phase method. The solid-phase synthesis of samples was carried out from decrepitated gadolinium (III) and tellurium (IV) oxides, strontium, and barium carbonates according to the standard ceramic technology. The synthesis was carried out in the temperature range of 800-1100 °C. The samples obtained were confirmed by X-ray phase analysis. X-ray phase analysis was carried out on an Empyrean instrument in the XRDML Pananalitical format. The intensity of the diffraction maxima was estimated on a 100-point scale. X-ray diffraction patterns indexing of the powder of gadolinium tellurites — alkaline earth metals studied were carried out by the homology method. The reliability and correctness of the results of indexing the X-ray diffraction patterns are confirmed by the good agreement between the experimental and calculated values of the interplanar distances (d) and the agreement between the values of the X-ray and pycnometric densities. It was found that compounds GdSrTeO4.5 and GdBaTeO4.5 crystallize in the monoclinic system and have the unit cell parameters, namely GdSrTeO4.5 — a = 12.7610, b = 10.4289, c = 8.6235 Å, V° = 1141.83 Å3, β = 95.77°, Z = 5, ρrent. = 3.22, ρpikn. = (3.10±0.09) g/cm3; GdBaTeO4.5 — a = 15.7272, b = 15.8351, c = 7.1393 Å, V° = 1769.72 Å3, β = 95.53°, Z = 8, ρrent = 3.71, ρpick = (3.61±0.10) g/cm3. Using the Landiya method, the standard heat capacities of the compounds were estimated from the calculated values of the standard entropies, and the temperature dependences of the heat capacities of the gadolinium tellurites synthesized were determined in the temperature range of 298–850 K.

Pottery of Early Iron Age from the Glinjeni II-La Șanț (North-Western Pontic Sea Region): Composition, Technology and Raw Material Sources

Transition to the Early Iron Age was marked by the appearance of innovations such as iron technology and changes in the lifestyle of local societies on the territory of the North-Western Pontic Sea region. One of the most interesting sites of this period is the Glinjeni II-La Șanț fortified settlement, located in the Middle Dniester basin (Republic of Moldova). Materials of different cultural traditions belonged to the Cozia-Saharna culture (10th–9th cc. BC) and the Basarabi-Șoldănești culture (8th–beginning of 7th cc. BC) were found on this site. The article presents the results of a multidisciplinary approach to the study of ceramic sherds from these archaeological complexes and cultural layers as well as raw clay sources from this area. The archaeometry analysis, such as the XRF-WD, the thin section analysis, SEM-EDX of ceramics, m-CT of pottery were carried out. The study of ancient pottery through a set of mineralogical and geochemical analytic methods allowed us to obtain new results about ceramic technology in different chronological periods, ceramic paste recipes and firing conditions. Correlation of archaeological and archaeometry data of ceramics from the Glinjeni II-La Șanț site gives us the possibility to differ earlier and later chronological markers in the paste recipes of pottery of 10th–beginning of 7th cc. BC in the region of the Middle Dniester basin.