Tetragonal phases

In all appHcations involving zirconia, the thermal instabiHty of the tetragonal phase presents limitations especially for prolonged use at temperatures greater than - 1000° C or uses involving thermal cycling. Additionally, the sensitivity of Y—TZP ceramics to aqueous environments at low temperatures has to be taken into account. High raw material costs have precluded some appHcations particularly in the automotive industry. 

Oxides such as CaO, MgO, and Y2O2 are added to Zr02 to stabili2e the tetragonal phase at temperatures below the tetragonal to monoclinic phase-transition temperature. Without stabili2et, the phase transition occurs spontaneously at temperatures below 850—1000°C, and no fracture toughness enhancement occurs (25). 

Figure 6.4 Crystal structure of ar-tetragonal boron. This was originally thought to be B50 (4Bi2 + 2B) but is now known to be either B50C2 or B50N2 in which the 2C (or 2N) occupy the 2(b) positions the remaining 2B are distributed statistically at other vacant sites in the lattice. Note that this reformulation solves three problems which attended the description of the or-tetragonal phase as a crystalline modification of pure B ...

When 0.4 < x < 0.53, an orthorhombic phase is observed in the AgxNb02+xFi.x system. This phase undergoes a phase transition at 900°C that leads to the formation of a tetragonal phase, which crystallizes in a tetragonal tungsten bronze-type structure with cell parameters a = 12.343 and c = 3.905 A. When 0.82 < x < 1, solid solutions based on AgNb03 were found, which crystallize in a perovskite-type structure. 

In all cases, broad diffuse reflections are observed in the high interface distance range of X-ray powder diffraction patterns. The presence of such diffuse reflection is related to a high-order distortion in the crystal structure. The intensity of the diffuse reflections drops, the closer the valencies of the cations contained in the compound are. Such compounds characterizing by similar type of crystal structure also have approximately the same type of IR absorption spectra [261]. Compounds with rock-salt-type structures with disordered ion distributions display a practically continuous absorption in the range of 900-400 cm 1 (see Fig. 44, curves 1 - 4). However, the transition into a tetragonal phase or cubic modification, characterized by the entry of the ions into certain positions in the compound, generates discrete bands in the IR absorption spectra (see Fig. 44, curves 5 - 8). 

The phase relationship between the most commonly known tetragonal phase CaC2-I and phase(s) II (or III) is still in question. CaC2-I transforms reversibly into the cubic phase IV, as does the phase (II -r) III. It is interesting to note that the cubic phase IV seems to have a memory for its respective precursor phase (III or I) that is regained after cooling down phase IV. The synthesis of... 

W0x-Zr02 samples with surface densities above 5-6 W-atoms nm contain only the metastable tetragonal phase (Figure 4), but pure Zr02 contains only the thermodynamically stable monoclinic phase. This apparent saturation coverage is higher than... 

---