Properties of Na0.5Bi0.5TiO3 Ceramics Modified with Fe and Mn.

Na0.5Bi0.5TiO3 (NBT) and Fe- and Mn-modified NBT (0.5 and 1 mol%) ceramics were synthesized by the solid-state reaction method. The crystal structure, dielectric and thermal properties of these ceramics were measured in both unpoled and poled states. Neither the addition of iron/manganese to NBT nor poling changed the average crystal structure of the material; however, changes were observed in the short-range scale. The changes in shapes of the Bragg peaks and in their 2Θ-position and changes in the Raman spectra indicated a temperature-driven structural evolution similar to that in pure NBT. It was found that both substitutions led to a decrease in the depolarization temperature Td and an increase in the piezoelectric coefficient d33. In addition, applying an electric field reactivated and extended the ferroelectric state to higher temperatures (Td increased). These effects could be the result of: crystal structure disturbance; changes in the density of defects; the appearance of (FeTi'-), (Mn'Ti-V••O) and (Mn″Tii-V••O )-microdipoles; improved domain reorientation conditions and instability of the local polarization state due to the introduction of Fe and Mn into the NBT; reinforced polarization/domain ordering; and partial transformation of the rhombohedral regions into tetragonal ones by the electric field, which supports a long-range ferroelectric state. The possible occupancy of A- and/or B-sites by Fe and Mn ions is discussed based on ionic radius/valence/electronegativity principles. The doping of Fe/Mn and E-poling offers an effective way to modify the properties of NBT.

New Nitride Nanoceramics from Synthesis-Mixed Nanopowders in the Composite System Gallium Nitride GaN-Titanium Nitride TiN.

Presented is a study on the preparation, via original precursor solution chemistry, of intimately mixed composite nanocrystalline powders in the system gallium nitride GaN-titanium nitride TiN, atomic ratio Ga/Ti = 1/1, which were subjected to high-pressure (7.7 GPa) and high-temperature (650, 1000, and 1200 °C) sintering with no additives. Potential equilibration toward bimetallic compounds upon mixing of the solutions of the metal dimethylamide precursors, dimeric {Ga[N(CH3)2]3}2 and monomeric Ti[N(CH3)2]4, was studied with 1H- and 13C{H}-NMR spectroscopy in C6D6 solution. The different nitridation temperatures of 800 and 950 °C afforded a pool of in situ synthesis-mixed composite nanopowders of hexagonal h-GaN and cubic c-TiN with varying average crystallite sizes. The applied sintering temperatures were either to prevent temperature-induced recrystallization (650 °C) or promote crystal growth (1000 and 1200 °C) of the initial powders with the high sintering pressure of 7.7 GPa having a detrimental effect on crystal growth. The powders and nanoceramics, both of the composites and of the individual nitrides, were characterized if applicable by powder XRD, SEM/EDX, Raman spectroscopy, Vicker's hardness, and helium density. No evidence was found for metastable alloying of the two crystallographically different nitrides under the applied synthesis and sintering conditions, while the nitride domain segregation on the micrometer scale was observed on sintering. The Vicker's hardness tests for many of the composite and individual nanoceramics provided values with high hardness comparable with those of the individual h-GaN and c-TiN ceramics.