Effect of AlN and Al2O3 additions on the phase relationships and morphology of SiC Part II: Microstructural observations

Additions of AlN and Al₂O₃ to -SiC hot pressed at 2100°C strongly effect the - to -SiC phase transformation and the resultant -SiC polytypes which are formed. Scanning and transmission electron microscopy were utilized to investigate the microstructural changes occurring in SiC due to these additions and to correlate these observations to their mechanical properties. The results suggest that Al₂O₃ additions stabilize the formation of the 6H-polytype of -SiC which grows rapidly into an elongated plate-like morphology, while AlN additions stabilize the 2H-polytype of -SiC resulting in fine equiaxed 2H-SiC: AlN solid solution grains. It is speculated that the elongated growth of 6H-SiC with Al₂O₃ additions can be controlled through the simultaneous addition of AlN. The formation of 2H-SiC : AlN solid solution grains inhibits the growth of the 6H-SiC grains since AlN(2H) will not go into solid solution in the SiC(6H) structure, effectively pinning the growth of the 6H-SiC grains.     

Solubility Limits of α'-SiAION Solid Solutions in the System Si,Al,Y/N,O

The solubility limit of α'-SiAION solid solutions on the Si₃N₄─YN:3AIN composition join in the system Si₃N₄─YN─AIN has been determined at 1800°C. The end members of these solid solutions are Y_0.43Si_10.7Al_1.3N₁₆ and Y_0.8Si_9.6Al_2.4N₁₆. Unit-cell dimensions of the α'-SiAION solid solutions in the system Si,Al,Y/N,O can be expressed as follows: a _o(Å) = 7.752 + 0.045 m + 0.009 n , c _o(Å) = 5.620 + 0.048 m + 0.009 n , where the α'-SiAION solid solution has the formula Y _x Si_{12-( m+n )}Al _m+n N_{16- n} O _n . The single-phase boundary of the solid solution α'-SiAION on the composition triangle Si₃N₄─YN:3AIN─AIN:Al₂O₃ is delineated. The present paper also reports the phase relationships involving α'-SiAION.     

Solid-Liquid Reactions in the System Si3N4–β-SiAlON–Y3Al5O12

Solid-liquid equilibria in the system Si,Al,Y/N,0 were determined for the compatibility triangle bounded by the β-SiAlON solid-solution line and the compound Y₃Al₅O₁₂. X-ray diffraction was used to determine the crystalline phases present in the equilibrated, rapidly cooled specimens. The liquid phase was quantified with volume fraction measurements performed on scanning electron micrographs. The solid-liquid tie lines at 1650° and 1750°C were established from lattice parameters of the β-SiAlON phase and from the amount of liquid phase in equilibrium with the crystalline solid. The liquid phase was crystallized to verify the location of the starting composition.     

Cubic-to-Tetragonal (t') Transformation in Zirconia-Containing Systems

The coexistence of the cubic fluorite and tetragonal phases in rapidly quenched samples was studied in the ZrO₂-MO_1.5 systems for M = Sc, In, Y, and rare earths (R). Spontaneous transformation from metastable cubic phase was triggered at room temperature by a mechanical force. Isolated tetragonal platelets in the cubic matrix were bounded by [101] habit planes and contained anti-phase boundaries. The tetragonality decreased with stabilizer content and vanished at around 18 mol% for M = Y and R, 23 mol% for M = Sc, and 25 mol% for M = In, all at room temperature. With increasing temperature, the tetragonality initially increased because of anisotropic thermal expansion, then decreased rapidly, after reaching a maximum, as the temperature for the tetragonal-to-cubic transformation was approached. Being a first-order martensitic transformation, the cubic-to-tetragonal transformation is accompanied by a discontinuous change of tetragonality and a hysteresis loop as the temperature or composition passes through the equilibrium value.     

Subsolidus Phase Relationships in Part of the System Si,Al,Y/N,O: The System Si3N4─AIN─YN─Al2O3─Y2O3

The subsolidus phase relationships in the system Si,Al,Y/N,O were determined. Thirty-nine compatibility tetrahedra were established in the region Si₃N₄─AIN─Al₂O₃─Y₂O₃. The subsolidus phase relationships in the region Si₃N₄─AIN─YN─Y₂O₃ have also been studied. Only one compound, 2YN:Si₃N₄, was confirmed in the binary system Si₃N₄─YN. The solubility limits of the α'─SiAION on the Si₃N₄─YN:3AIN join were determined to range from m = 1.3 to m = 2.4 in the formula Y _{m /3}Si_{12- m} Al _m N₁₆. No quinary compound was found. Seven compatibility tetrahedra were established in the region Si₃N₄─AIN─YN─Y₂O₃.     

Effect of Crystallization of the Grain-Boundary Phase on the Thermal Diffusivity of a Sialon Ceramic

Crystallization of the glassy grain-boundary phase in a series of sialon ceramics fabricated using a range of hot-pressing schedules increased the thermal diffusivity at room temperature by an average of ∼10%. For samples made by a given hot-pressing schedule, the relative difference in thermal diffusivity between composites containing a glassy grain-boundary phase and those in which this phase had crystallized decreased with increasing temperature. This behavior is attributed to enhanced phonon scattering in the crystalline grain-boundary phase.     

Formation of β-Silicon Nitride Crystals from (Si,Al,Mg,Y)(O,N) Liquid: I, Phase, Composition, and Shape Evolutions

Precipitation, growth, and coarsening of Si₃N₄ crystals in (Si,Al,Mg,Y)(O,N) liquids at 1680°C has been studied. The initial nucleation of β-Si₃N₄ occurs mostly on α-Si₃N₄ because of the very high supersaturation of the liquid. After a brief period of growth, the crystals then undergo accelerated coarsening, decreasing the crystal concentration by almost 100 times with little change in the total crystal volume. Meanwhile, the crystals gradually transform from β-Si₃N₄, by substituting Si-N with Al-O, to β'-SiAlON of various compositions. The evolution of aspect ratio strongly depends on the Si/(Al,Mg,Y) ratio, which is rationalized by cation segregation to the interface driven by the acidity-basicity differential between the liquid and the crystal.     

Kinetics of β-Si3N4 Grain Growth in Si3N4 Ceramics Sintered under High Nitrogen Pressure

The kinetics of anisotropic β-Si₃N₄ grain growth in silicon nitride ceramics were studied. Specimens were sintered at temperatures ranging from 1600° to 1900°C under 10 atm of nitrogen pressure for various lengths of time. The results demonstrate that the grain growth behavior of β-Si₃N₄ grains follows the empirical growth law Dⁿ– D₀ⁿ = kt , with the exponents equaling 3 and 5 for length [001] and width [210] directions, respectively. Activation energies for grain growth were 686 kJ/mol for length and 772 kJ/mol for width. These differences in growth rate constants and exponents for length and width directions are responsible for the anisotropy of β-Si₃N₄ growth during isothermal grain growth. The resultant aspect ratio of these elongated grains increases with sintering temperature and time.     

Solid-Liquid Reaction in the Si3N4-AlN-Y2O3 System under 1 MPa of Nitrogen

The melting behaviors of selected compositions in the Si₃N₄-AlN-Y₂O₃ system were determined under 1 MPa of nitrogen. The phase diagrams of the ternary and their binary systems are presented. The lowest melting composition of the ternary system contains 15 mol % Si₃N₄, 25 mol % AIN, and 60 mol % Y₂O₃ and has a melting temperature of 1650°C. The binary eutectic compositions and temperatures are 15 mol % Si₃N₄ and 85 mol % Y₂O₃ at 1720°C, and 20 mol % AIN and 80 mol% Y₂O₃ at 1730°C.