Thermal Conductivity of β-Si3N4: II, Effect of Lattice Oxygen

Dense β-Si₃N₄ with various Y₂O₃/SiO₂ additive ratios were fabricated by hot pressing and subsequent annealing. The thermal conductivity of the sintered bodies increased as the Y₂O₃/SiO₂ ratio increased. The oxygen contents in the β-Si₃N₄ crystal lattice of these samples were determined using hot-gas extraction and electron spin resonance techniques. A good correlation between the lattice oxygen content and the thermal resistivity was observed. The relationship between the microstructure, grain-boundary phase, lattice oxygen content, and thermal conductivity of β-Si₃N₄ that was sintered at various Y₂O₃/SiO₂ additive ratios has been clarified.     

Microstructural Evolution of Gas-Pressure-Sintered Si3N4 with Yb2O3 as a Sintering Aid

Microstructural evolution of gas-pressure-sintered Si₃N₄ with Yb₂O₃ as a sintering aid was observed. Microstructures typical for in situ toughened Si₃N₄, i.e., large elongated grains randomly distributed in a fine matrix, were observed. However, the size of the elongated grains near the surface was much larger than that at the center, resulting in two distinct regions: an inner region and an outer region. The smaller the amount of Yb₂O₃ added, the larger the difference in the size of the elongated grains between the outer and inner regions. The difference between microstructures was diminished when 16 wt% Yb₂O₃ was added. The microstructural change with Yb₂O₃ content was attributed to the evaporation of Yb-containing liquid phase from the surface.     

Phase Evolution in Heat-Treated Si3N4 with Additions of Yb2O3

The heat treatment of silicon nitride (Si₃N₄) ceramics with additions of 8, 12, and 16 wt% Yb₂O₃ was carried out at different temperatures and the evolution of grain boundary (GB) phase was investigated systematically by X-ray diffraction (XRD) as well as scanning electron and transmission electron microscopic analyses. XRD results reveal that the extent and the ease of GB crystallization increase with increasing the Yb₂O₃ content, and that high heat-treatment temperatures in general favor crystallization of the quaternary compounds such as the Yb₄Si₂O₇N₂ phase. These results provide an insight into the GB phase evolution in the Yb-system Si₃N₄ ceramics subjected to a postsintering heat treatment.     

Oxidation and Strength Retention of Monolithic Si3N4 and Nanocomposite Si3N4-SiC with Yb2O3 as a Sintering Aid

The oxidation behaviors of monolithic Si₃N₄ and nanocomposite Si₃N₄-SiC with Yb₂O₃ as a sintering aid were investigated. The specimens were exposed to air at temperatures between 1200° and 1500°C for up to 200 h. Parabolic weight gains with respect to exposure time were observed for both specimens. The oxidation products formed on the surface also were similar, i.e., a mixture of crystalline Yb₂Si₂O₇ and SiO₂ (cristobalite). However, strength retention after oxidation was much higher for the nanocomposite Si₃N₄-SiC compared to the monolithic Si₃N₄. The SiC particles of the nanocomposite at the grain boundary were effective in suppressing the migration of Yb³⁺ ions from the bulk grain-boundary region to the surface during the oxidation process. As a result, depletion of yttribium ions, which led to the formation of a damaged zone beneath the oxide layer, was prevented.     

Reaction-Formed Porous Yb4Si2N2O7 Materials with Uniform Open-Cell Network Structure

A novel porous Yb₄Si₂O₇N₂ material with uniform open-cell network structure was fabricated from the reaction between Si₃N₄, Yb₂O₃, and SiO₂. The formation of Yb₄Si₂O₇N₂ during heating was studied using X-ray diffractometry. The porous structure was characterized using scanning electron microscopy and mercury porosimeter. It is shown that the formation of Yb₄Si₂O₇N₂ phase starts at ∼1150°C and completes at 1350°C for 4 h, accompanied by the development of open-cell network structure. The necks between Yb₄Si₂O₇N₂ particles become much thicker with increasing temperature because of the coarsening of Yb₄Si₂O₇N₂ particles, thus leading to a uniform three-dimensional network structure. Furthermore, the pore size can be well controlled by adjusting reacting temperature and altering atmosphere.     

Thermal Conductivity of Gas-Pressure-Sintered Silicon Nitride

Si₃N₄ with high thermal conductivity (120 W/(m^.K)) was developed by promoting grain growth and selecting a suitable additive system in terms of composition and amount. β-Si₃N₄ doped with Y₂O₃-Nd₂O₃ (YN system) or Y₂O₃-A1₂O₃ (YA system) was sintered at 1700°-2000°C. Thermal conductivity increased with increased sintering temperature because of decreased two-grain junctions, as a result of grain growth. The effect of the additive amount on thermal conductivity with the YN system was rather small because increased additive formed multigrain junctions. On the other hand, with the YA system, thermal conductivity considerably decreased with increased additive amount because the aluminum and oxygen in the YA system dissolved into β-Si₃N₄ grains to form a β-SiAlON solid solution, which acted as a point defect for phonon scattering. The key processsing parameters for high thermal conductivity of Si₃N₄ were the sintering temperature and additive composition.     

Evaluation of Glassy Phase in Sintered Silicon Nitride by Low-Temperature Specific Heat Measurements

The specific heat of HIP sintered Si₃N₄ with 3 mol% Y₂O₃ and 3 mol% Al₂O₃ additives was measured at different temperatures ranging from 2 to 10 K, in order to confirm the presence of a glassy phase in the sintered body. The grainboundary glassy phase in the sintered Si₃N₄ was evaluated by specific heat measurements. The difference between the experimental value and the lattice specific heat calculated from the Debye theory confirmed the existence of a glassy phase in sintered Si₃N₄.     

Influence of Rare-Earth Additives on Wear Properties of Hot-Pressed Silicon Nitride Ceramics under Dry Sliding Conditions

The influence of different rare-earth sintering additives (Y, Yb, Lu) on the wear properties of Si₃N₄ ceramics was investigated during sliding contact without lubricant. The kind of rare-earth additives was shown to have a significant effect on the wear behavior for contact sliding under the present testing conditions. Samples sintered with Y₂O₃ as the sintering additive showed evidence of fracture type wear although this was not observed in samples sintered with Yb₂O₃ and Lu₂O₃. These smaller rare earths lead to higher grain boundary bonding strength and superior high-temperature properties and resulted in higher wear resistance. These results showed that the wear properties of Si₃N₄ ceramics could be tailored by judicious selection of the sintering additives.     

Processing and Thermal Conductivity of Sintered Reaction-Bonded Silicon Nitride: (II) Effects of Magnesium Compound and Yttria Additives

The effects of the magnesium compound and yttria additives on the processing, microstructure, and thermal conductivity of sintered reaction-bonded silicon (Si) nitride (SRBSN) were investigated using two additive compositions of Y₂O₃–MgO and Y₂O₃–MgSiN₂, and a high-purity coarse Si powder as the starting powder. The replacement of MgO by MgSiN₂ leads to the different characteristics in RBSN after complete nitridation at 1400°C for 8 h, such as a higher β-Si₃N₄ content but finer β-Si₃N₄ grains with a rod-like shape, different crystalline secondary phases, lower nitrided density, and coarser porous structure. The densification, α→β phase transformation, crystalline secondary phase, and microstructure during the post-sintering were investigated in detail. For both cases, the similar microstructure observed suggests that the β-Si₃N₄ nuclei in RBSN may play a dominant role in the microstructural evolution of SRBSN rather than the intergranular glassy chemistry during post-sintering. It is found that the SRBSN materials exhibit an increase in the thermal conductivity from ∼110 to ∼133 (Wm·K)⁻¹ for both cases with the increased time from 6 to 24 h at 1900°C, but there is almost no difference in the thermal conductivity between them, which can be explained by the similar microstructure. The present investigation reveals that as second additives, the MgO is as effective as the MgSiN₂ for enhancing the thermal conductivity of SRBSN.     

Change in Oxygen Content of Y2O3-Nd2O3-Doped Silicon Nitride During Firing

The oxygen content of silicon nitride with 1 mol% Y₂O₃—Nd₂O₃ additive was measured after firing to determine the compositional change during gas-pressure sintering. Oxygen content decreases from 2.5 to 0.94 wt% during firing for 4 h at 1900°C and 10-MPa pressure in N₂. This decrease in oxygen results from the release of SiO gas generated by a thermaldecomposition reaction between Si₃N₄ and SiO₂. The resultant sintered silicon nitride material contains less than 1 wt% oxygen.     

Reaction Synthesis of Magnesium Silicon Nitride Powder

The synthesis of magnesium silicon nitride (MgSiN₂) by direct nitridation of a Si/Mg₂Si/Mg/Si₃N₄ powder mixture is described. A nucleation period at 550°C and stepwise heat-treatment schedule up to 1350°C was adopted for the synthesis of MgSiN₂ powder, based on TG-DTA measurements. The influence of the ratio of constituents on the final phase composition also has been studied. The content of magnesium and silicon in the starting powder should fulfill the conditions Mg₂Si/Mg ≥ 3 and Si₃N₄/Si_tot≥ 0.5 to obtain single-phase MgSiN₂. The silicon particle size of <0.5 μm is preferable to decrease the time of nitridation. The oxygen content of as-synthesized powders is in the range 0.9–1.2 wt%. However, the oxygen content of MgSiN₂ powder decreases further by the addition of 2 wt% CaF₂ or 0.75 wt% carbon and reaching the lowest value of 0.45 wt% oxygen after carbothermal reduction in an alumina-tube furnace.     

Microstructure Tailoring for High Thermal Conductivity of β-Si3N4 Ceramics

β-Si₃N₄ ceramics sintered with Yb₂O₃ and ZrO₂ were fabricated by gas-pressure sintering at 1950°C for 16 h changing the ratio of "fine" and "coarse" high-purity β-Si₃N₄ raw powders, and their microstructures were quantitatively evaluated. It was found that the amount of large grains (greater than a few tens of micrometers) could be drastically reduced by mixing a small amount of "coarse" powder with a "fine" one, while maintaining high thermal conductivity (>140 W·(m·K)⁻¹). Thus, this work demonstrates that it is possible for β-Si₃N₄ ceramics to achieve high thermal conductivity and high strength simultaneously by optimizing the particle size distribution of raw powder.     

Sintering of Si3N4-Y2O3 Under Nitrogen Pressure

This study shows that the amount ofAl₂O₃ needed to form high density Si₃N₄-15Y₂-O₃ samples can be reduced by using high surface area Si₃N₄ powder and high N₂ overpressure (high sintering temperatures) during the sintering process. The reduction in AI₂O₃ content results in improved oxidation resistance of the sintered samples.     

Hot Isostatic Pressing of Silicon Nitride with Boron Nitride, Boron Carbide, and Carbon Additions

Si₃ N₄ test bars containing additions of BN, B₄C, and C, were hot isostatically pressed in Ta cladding at 1900° and 2050°C to 98.9% to 99.5% theoretical density. Room-temperature strength data on specimens containing 2 wt% BN and 0.5 wt% C were comparable to data obtained for Si₃ N₄ sintered with Y₂O₃, Y₂O₃ and Al₂O₃, or ZrO₂. The 1370°C strengths were less than those obtained for additions of Y₂O₃ or ZrO₂ but greater than those obtained from a combination of Y₂O₃ and Al₂O₃. Scanning electron microscope fractography indicated that, as with other types of Si₃N₄, roomtemperature strength was controlled by processing flaws. The decrease in strength at 1370°C was typical of Si₃N₄ having an amorphous grainboundary phase. The primary advantage of non-oxide additions appears to be in facilitating specimen removal from the Ta cladding.     

Pressureless Sintering of α-Si3N4 Porous Ceramics Using a H3PO4 Pore-Forming Agent

A new method for preparing high bending strength porous silicon nitride (Si₃N₄) ceramics with controlled porosity has been developed by using pressureless sintering techniques and phosphoric acid (H₃PO₄) as the pore-forming agent. The fabrication process is described in detail and the sintering mechanism of porous ceramics is analyzed by the X-ray diffraction method and thermal analysis. The microstructure and mechanical properties of the porous Si₃N₄ ceramics are investigated, as a function of the content of H₃PO₄. The resultant high porous Si₃N₄ ceramics sintered at 1000°–1200°C show a fine porous structure and a relative high bending strength. The porous structure is caused mainly by the volatilization of the H₃PO₄ and by the continous reaction of SiP₂O₇ binder, which could bond on to the Si₃N₄ grains. Porous Si₃N₄ ceramics with a porosity of 42%–63%, the bending strength of 50–120 MPa are obtained.     

Processing of Concentrated Aqueous Silicon Nitride Slips by Slip Casting

The optimization of concentrated Si₃N₄ powder aqueous slurry properties to achieve high packing density slipcast compacts and subsequent high sintered densities was investigated. The influence of pH, sintering aid powder (6% Y₂O₃, 4% Al₂O₃), NH₄PA dispersant, and Si₃N₄ oxidative thermal treatment was determined for 32 vol% Si₃N₄ slurries. The results were then utilized to optimize the dispersion properties of 43 vol% solids Si₃N₄-sintering aid slurries. Calcination of the Si₃N₄ powder was observed to result in significantly greater adsorption of NH₄PA dispersant and effectively reduced the viscosity of the 32 vol% slurries. Lower viscosities of the optimized dispersion 43 vol% Si₃N₄-sintering aid slurries resulted in higher slipcast packing density compacts with smaller pore sizes and pore volumes, and corresponding higher sintered densities.     

The Role of Cerium Orthosilicate in the Densification of Si3N4

The existence of compounds between Si₃N₄-CeO₂ and Si₃N₄-Ce₂O₃ was investigated for firing temperatures of 1600° to 1700°C. The two new monoclinic compounds found were Ce₂O₃·2Si₃N₄ with lattice parameters a = 16.288, b = 4.848, and c =7.853 Å and β=91.54° and Ce₄Si₂O₇N₂ with lattice parameters a = 10.360, b = 10.865, and c =3.974 Å and β=90.33°. Cerium orthosilicate (Ce 4.67 (SiO₄)₃O) is present during firing as a glassy intermediate phase which promotes sintering and densification and then reacts with silicon nitride to form cerium silicon oxynitrde (CeSiO₂N).     

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.     

Bond Energetics at Intergranular Interfaces in Alumina-Doped Silicon Nitride

In Si₃N₄ ceramics sintered with Al₂O₃, the interfacial strength between the intergranular glass and the reinforcing grains has been observed to increase with increases in the aluminum and oxygen content of the epitaxial β-Si_{6- z} Al _z O _z N_{8– z} layer that forms on the Si₃N₄ grains. This has been attributed to the formation of a network of strong bonds (cross bonds) that span the glass-crystalline interface. This proposed mechanism is considered further in light of first-principles atomic cluster calculations of the relative stabilities of bridge and threefold-bonded atomic fragments chosen to represent compositional changes at the glass/Si₃N₄ grain interface. Calculated binding energies indicate Al-N binding is favorable at the Si₃N₄ grain surface, where aluminum occupancy can promote the growth of SiAlON, further enhancing the cross-bonding mechanism of interfacial strengthening.     

Electrically Conductive CNT-Dispersed Silicon Nitride Ceramics

Carbon nanotube (CNT)-dispersed Si₃N₄ ceramics with electrical conductivity were developed based on the lower temperature densification technique, in which the key point is the addition of both TiO₂ and AlN as well as Y₂O₃ and Al₂O₃ as sintering aids. This new ceramic with a small amount of CNTs exhibits very high electrical conductivity in addition to high strength and toughness. Since Si₃N₄ ceramics with Y₂O₃–Al₂O₃–TiO₂–AlN were originally used as a wear material, electrically conductive Si₃N₄ ceramics are expected to be applied for high-performance static-electricity-free bearings for aerospace and other high-performance components.