Role of nanopowder agglomerates in forming the structure and properties of ceramic materials

A comparative analysis of agglomerates obtained by spray drying and granulation methods and consolidated materials based on them was carried out. The paper provides the results obtained when studying zirconia nanopowders granulated in water medium with an agar agar additive obtained by chemical precipitation with zirconia partially stabilized by yttrium oxide (2.5 mol.%), and TZ-3Y-E powder manufactured by Tosoh Corp. (Japan) that was prepared by spray drying. Agglomerates as well as microsections and fractures of samples were studied by scanning electron, optical, atomic force microscopy, and Raman spectroscopy. The crack resistance coefficient (K1с) of samples was determined by indenting the polished surface of microsections with a Vickers pyramid. The specific surface of the powders measured by nitrogen thermal desorption during granulation remains unchanged indicating a significant open porosity of agglomerates obtained. With increasing compacting pressure under conditions of semi-dry compaction with an aqueous solution of PVA as a binder, agglomerates and even aggregates of granulated powders are destroyed, K1с increases with increasing compaction pressure and the accompanying material microstructure grinding. Powders agglomerated using spray drying break up much less intensively, K1с does not change with increasing pressure. The studies conducted allow us to agree with the authors pointing to the fractal nature of agglomerates obtained from chemically precipitated nanopowders without the use of spray drying. The use of granulated nanopowders in semi-dry compaction with the application of high pressures makes it possible to destroy not only agglomerates, but also aggregates, and to obtain nanostructured ceramics with grain sizes close to the size of initial particles.

Effects of Calcium Oxide and Magnesium Oxide Stabilizing Agents on the Critical Transformation Size of Tetragonal Zirconia

The preparation of tetragonal zirconia nanopowders by sol–gel method using zirconium oxychloride as raw material, ammonia water and sodium hydroxide solution as precipitant, and calcium oxide or magnesium oxide powders as stabilizing agents is described. After suction filtration, drying, and calcination, tetragonal zirconia nanopowders with different particle size and tetragonal phase content were obtained. The particle size and phase composition of the powders are characterized by using a laser particle size analyzer and an X-ray diffractometer, and the tetragonal phase content and grain size are calculated from the crystal plane formula and Scherrer formula. The analysis of the relationship between the tetragonal phase content and the particle size of the zirconia nanopowders stabilized by calcium oxide and magnesium oxide at room temperature reveals the inhibitory effect of the stabilizing agents on the growth of zirconia grains. The stabilized zirconia nanopowder is finer than unstabilized zirconia nanopowder, and the particle distribution is more uniform in the former. The stabilizing effect of calcium oxide is superior to that of magnesium oxide; the critical transformation size of the zirconia grains stabilized by calcium oxide is the largest, and that of unstabilized zirconia is the smallest. The critical transformation size of calcium oxide-stabilized, magnesium oxide-stabilized, and unstabilized zirconia nanopowders is 18–22.6 nm, 24–28 nm, and 26–33.6 nm, respectively. Under the same calcination condition, the calcium oxide-stabilized zirconia nanopowder retains the highest tetragonal phase content at room temperature.

Nanopowders of Yttria-Stabilized Zirconia Doped with Rare Earth Elements as Adsorbents of Humic Acids

The aim of the investigations was to use, for the first time, zirconia nanopowders stabilized with yttria (YSZ) and rare element oxides (YSZ-Nd, YSZ-Gd) for removal of humic acids (HA) from aqueous solutions. Nanopowders were synthesized by means of hydrothermal crystallization and characterized using scanning electron microscope (SEM) with energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Fourier transform infrared (FT-IR) methods and analysis of zeta potential. The adsorption processes analysis was carried out in a series of experiments depending on: initial concentration of humic acids, contact time, pH and mass of the used adsorbent. It was found, that the YSZ-Nd exhibits strong and much higher effectiveness of HA adsorption than YSZ and YSZ-Gd. The HA adsorption rate reached 96.8% for YSZ-Nd dosage of 100 mg, pH 4, and 15 min reaction time and for HA initial concentration equal to 25 mg/L. According to the Langmuir model simulation, the maximum adsorption capacity of HA on YSZ-Nd at pH 4 was calculated to be 2.95 mg/g. Changes in the FT-IR spectra of YSZ-Nd confirmed humic acids’ adsorption on the tested nanopowders, by the presence of additional bands representing carboxylic, alcohol, carbonyl and amino groups in humic acid structure. These functional groups could represent humic acids binding on the YSZ, YSZ-Nd or YSZ-Gd surfaces.