The System Si3N4-SiO2-Y2O3

Subsolidus phase relations were established in the system Si₃N₄-SiO₂-Y₂O₃. Four ternary compounds were confirmed, with compositions of Y₄Si₂O₇N₂, Y₂Si₃O₃N₄, YSiO₂N, and Y₁₀(SiO₄)₆N₂. The eutectic in the triangle Si₃N₄-Y₂Si₂O₇-Y₁₀(SiO₄)₆N₂ melts at 1500°C and that in the triangle Si₂N₂O-SiO₂-Y₂Si₂O₇ at 1550°C. The eutectic temperature of the Si₃N₄-Y₂Si₂O₇ join was ∼ 1520°C.     

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.     

Phase Relations in the Si3N4-Rich Portion of the Si3N4–AlN–Al2O3–Y2O3

The phase relations in the Si₃N₄-rich portion of the Si₃N₄–AlN–Y₂O₃ rystem were investigated using hot-pressed bodies. The one-phase fields of β3 and α, the twophase fields of β+α, β+M (M=melilite), and α+M, and the three-phase fields of β+α+M were observed in the Si₃N₄-rich portion. The α- and β-sialons are not two different compounds but an allotropic transformation phase of the Si–Al–O–N system, and an α solid solution expands and stabilizes with increasing Y₂O₃ content. Therefore, the formulas of the two sialons should be the same.     

Nucleation and Growth of α'-SiAlON on α-Si3N4

Morphology, composition, and growth defects of α'-SiAION have been studied in a fine-grained material with an overall composition Y_0.33Si₁₀Al₂O₁N₁₅ prepared from α-Si₃N₄, AlN, Al₂O₃, and Y₂O₃ powders. TEM analysis has shown that fully grown α'-SiAloN grains always contain an α-Si₃N₄ core, implicating heterogeneous nucleation operating in the present system. The growth mode is epitaxial, despite the composition and lattice parameter difference between α-Si₃N₄ and α'-SiAlON. The inversion boundary that separates two domains in the seed crystal is seen to continue in the grown α'-SiAION. Lacking a special growth habit, the growth typically proceeds from more than one site on the seed crystal, and the different growth fronts impinge on each other to give an equiaxed appearance of α'-SiAlON. Misfit dislocations on the α/α'interface are identified as [0001] type ( b = 5.62 Å) and 1/3 [1 2 10] type ( b = 7.75 Å). These nucleation and growth characteristics dictate that microstructural control of α'-SiAlON must rest on the size distribution of the starting α-Si₃N₄ powder.     

High-Temperature Properties of Mixed α'/β'-SiAlON Materials

The mechanical behavior of mixed α'/β'-SiAlON materials was studied at elevated temperatures. Two different α'/β'-SiAlON compositions along the Si₃N₄-Y₂O₃9AlN composition line in the Si₃N₄-Al₂O₃AlN-YN3AlN plane (α'-SiAlON plane) were prepared using three different raw-material mixtures. Six different materials were obtained with significantly lower values in α'-SiAlON than expected. The high-temperature properties of the materials studied were influenced strongly by the chemical composition (α' content and grain-boundary phase) of the SiAlONs. A high content of α'-SiAlON was beneficial in terms of creep behavior of the materials. The same materials, however, were characterized by a considerably degradated fracture behavior at elevated temperatures in air because of a crack-growth process enhanced by the poor oxidation resistance of these materials. It was concluded that, despite some superior features of the materials studied, a long-term application of mixed α'/β'-SiAlON materials at 1400°C in air is problematical. A combination of all properties required for such applications was not observed. For that reason, it is suggested that the real high-temperature potential of these materials in air should be limited to temperatures <1300°C.     

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.     

Microstructure and Mechanical Properties of the in situβ-Si3N4/α'-SiAlON Composite

The in situ β-Si₃N₄/α'-SiAlON composite was studied along the Si₃N₄–Y₂O₃: 9 AlN composition line. This two phase composite was fully densified at 1780°C by hot pressing Densification curves and phase developments of the β-Si₃N₄/α'-SiAlON composite were found to vary with composition. Because of the cooperative formation of α'-Si AlON and β-Si₃N₄ during its phase development, this composite had equiaxed α'-SiAlON (∼0.2 μm) and elongated β-Si₃N₄ fine grains. The optimum mechanical properties of this two-phase composite were in the sample with 30–40%α', which had a flexural strength of 1100 MPa at 25°C 800 MPa at 1400°C in air, and a fracture toughness 6 Mpa·m^1/2. α'-SiAlON grains were equiaxed under a sintering condition at 1780°C or lower temperatures. Morphologies of the α°-SiAlON grains were affected by the sintering conditions.     

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.     

Subsolidus Phase Relationships in Si3N4–AlN–Rare-Earth Oxide Systems

The subsolidus phase relationships in Si₃N₄–AlN–rare-earth oxide (Me₂O₃ where Me=Nd, Sm, Gd, Dy, Er, and Yb) systems were studied. Solid-solution regions with the α-Si₃N₄ structure were delineated along the Si₃N₄–"Me₂O₃:9AIN" joins for all of the rare-earth oxide systems studied. The solubility limits of these solid solutions increased with decreasing size of the rare-earth ions.     

Formation of α-Si3N4 Solid Solutions in the System Si3N4-A1N-Y2O3

The subsolidus phase diagram of the quasiternary system Si₃N₄-AlN-Y₂O₃ was established. In this system α-Si₃N₄ forms a solid solution with 0.1Y₂O₃: 0.9 AIN. The solubility limits are represented by Y_0.33Si_10.5Al_1.5O_0.5N_15.5 and Y_0.67Si₉A1₃ON₁₅. At 1700°C an equilibrium exists between β-Si₃N₄ and this solid solution.     

Phase Relations and Stability Studies in the Si3N4-SiO2-Y2O3 Pseudoternary System

Composite powders were hot-pressed to determine the phase relations in the Si₃N₄-SiO₂-Y₂O₃ pseudoternary system. Four quaternary compounds, Si₃Y₂O₃N₄, YSiO₂N, Y₁₀Si₇O₂₃N₄, and Y₄Si₂O₇N₂, were identified. Studies of polyphase and single-phase materials in this system showed that these 4 compounds are unstable under oxidizing conditions. Materials within the Si₃N₄-Si₂N₂O-Y₂Si₂O₇ compatibility triangle precluded the unstable compounds, and are extremely resistant to oxidation.     

Sintering of Si3N4-Y2O3-Al2O3

Sintering kinetics of the system Si₃N4-Y2O₃-Al₂O3 were determined from measurements of the linear shrinkage of pressed disks sintered isothermally at 1500° to 1700°C. Amorphous and crystalline Si₃N₄ were studied with additions of 4 to 17 wt% Y₂O₃ and 4 wt% A1₂O₃. Sintering occurs by a liquid-phase mechanism in which the kinetics exhibit the three stages predicted by Kingery's model. However, the rates during the second stage of the process are higher for all compositions than predicted by the model. X-ray data show the presence of several transient phases which, with sufficient heating, disappear leaving mixtures of β ' -Si₃N₄ and glass or β '-Si₃N₄, α '-Si₃N₄, and glass. The compositions and amounts of the residual glassy phases are estimated.     

Influence of Phase Formation on Dielectric Properties of Si3N4 Ceramics

The influence of phase formation on the dielectric properties of silicon nitride (Si₃N₄) ceramics, which were produced by pressureless sintering with additives in MgO–Al₂O₃–SiO₂ system, was investigated. It seems that the difference in the dielectric properties of Si₃N₄ ceramics sintered at different temperatures was mainly due to the difference of the relative content of α-Si₃N₄, β-Si₃N₄, and the intermediate product (Si₂N₂O) in the samples. Compared with α-Si₃N₄ and Si₂N₂O, β-Si₃N₄ is believed to be a major factor influencing the dielectric constant. The high-dielectric constant of β-Si₃N₄ could be attributed to the ionic relaxation polarization.     

Phase Relationships in the Si3N4–SiO2–Lu2O3 System

Phase relationships in the Si₃N₄–SiO₂–Lu₂O₃ system were investigated at 1850°C in 1 MPa N₂. Only J-phase, Lu₄Si₂O₇N₂ (monoclinic, space group P 2₁/ c , a = 0.74235(8) nm, b = 1.02649(10) nm, c = 1.06595(12) nm, and β= 109.793(6)°) exists as a lutetium silicon oxynitride phase in the Si₃N₄–SiO₂–Lu₂O₃ system. The Si₃N₄/Lu₂O₃ ratio is 1, corresponding to the M-phase composition, resulted in a mixture of Lu–J-phase, β-Si₃N₄, and a new phase of Lu₃Si₅ON₉, having orthorhombic symmetry, space group Pbcm (No. 57), with a = 0.49361(5) nm, b = 1.60622(16) nm, and c = 1.05143(11) nm. The new phase is best represented in the new Si₃N₄–LuN–Lu₂O₃ system. The phase diagram suggests that Lu₄Si₂O₇N₂ is an excellent grain-boundary phase of silicon nitride ceramics for high-temperature applications.     

Hot-Pressing of Si3N4 with Y2O3 and Li2O as Additives

The rates of densification and phase transformation undergone by α-Si₃N₄ during hot-pressing in the presence of Y₂O₃, Y₂O₃−2SiO₂, and Li₂0−2Si0₂ as additives were studied. Although these systems behave less simply than MgO-doped Si₃N₄, the data can be interpreted during the early stages of hot-pressing as resulting from a solution-diffusion-reprecipitation mechanism, where the diffusion step is rate controlling and where the reprecipitation step invariably results in the formation of the β-Si₃N₄ phase.     

Preparation of Composite Particles by Pulsed Nd-YAG Laser Decomposition of [(CH3)2N]4Ti to TiN-Coat TiO2, Al2O3, or Si3N4 Powders

Irradiation of Ti[N(CH₃)₂]₄ by the 1.064-μm line of a pulsed Nd: YAG laser in the presence of TiO₂, Al₂O₃, or Si₃N₄ particles has been found to form amorphous deposits on the oxide particles. The resulting materials can be processed into TiN/TiO₂, TiN/Al₂O₃, or TiN/Si₃N₄ composites with the TiN component on the surface of the particles. The powders have been characterized by Raman spectroscopy and X-ray powder diffraction studies. The surface analysis of the composites by X-ray photoelectron spectroscopy and high-resolution electron microscopy is presented.     

Formation of N-phase and Phase Relationships in MgO–Si2N2O–Al2O3 System

Formation of N-phase in the system Mg,Si,Al/N,O was studied. Its composition was confirmed to be MgAl₂Si₄O₆N₄ (2Si₂N₂OMgAl₂O₄). Subsolidus phase relationships in the MgO–Si₂N₂O-Al₂O₃ system were determined. The results are discussed by comparing with two similar systems, CaO-and Y₂O₃–Si₂N₂O–Al₂O₃.     

Silicon Nitride Joining Using Silica and Yttria Ceramic Interlayers

Dense hot-pressed β-Si₃N₄ blocks were joined using both SiO₂ and SiO₂-Y₂O₃ powder slurries as bonding interlayers. The assembled specimens (Si₃N₄/interlayer/Si₃N₄) were heated in a flowing N₂ atmosphere in the temperature range of 1500°–1650°C. The joining interlayer was clearly distinguished from the Si₃N₄ bulk. The microstructure and the reaction products found in the bonding interlayer were very different in both compositions. Reactions occurring between the Si₃N₄ and the ceramic joining compositions have been explained based on existing diagrams of the YN–Si₃N₄-Y₂O₃-SiO₂ system.     

Properties of Si3N4 Produced by Nitriding Slip-Cast Si Containing Si3N4 Grog Additions

The properties of Si₃N₄ compositions produced by nitriding slip-cast Si bodies containing up to 16% Si₃N₄ grog were determined. The introduction of grog consistently lowered the densities, the room- and high-temperature strengths, and the resistance to oxidation. The open structure of the grog-containing mixes favored low-temperature gas-phase reactions leading to α-Si₃N₄ formation. In higher-density compositions containing predominantly Si, gas-liquid-solid reactions at higher temperatures produced a relatively greater content of the β phase.     

Synthesis and Properties of Porous Single-Phase β'-SiAlON Ceramics

Single-phase β'-SiAlON (Si_{6− z} Al _z O _z N_{8− z} , z = 0–4.2) ceramics with porous structure have been prepared by pressureless sintering of powder mixtures of á-Si₃N₄, AlN, and Al₂O₃ of the SiAlON compositions. A solution of AlN and Al₂O₃ into Si₃N₄ resulted in the β'-SiAlON, and full densification was prohibited because no other sintering additives were used. Relative densities ranging from 50%–90% were adjusted with the z -value and sintering temperature. The results of X-ray diffraction, scanning electron microscopy, and transmission electron microscopy analyses indicated that single-phase β'-SiAlON free from a grain boundary glassy phase could be obtained. Both grain and pore sizes increased with increasing z -value. Low z -value resulted in a relatively high flexural strength.