Processing and Thermal Conductivity of Sintered Reaction-Bonded Silicon Nitride. I: Effect of Si Powder Characteristics

This paper will present sintered reaction-bonded silicon nitride (SRBSN) material with a high thermal conductivity of 121 W·(m·K)⁻¹, which has been successfully prepared from a coarse Si powder with lower levels of oxygen and aluminum impurities, using a mixture of Y₂O₃ and MgSiN₂ as sintering additives, by nitriding at 1400°C for 8 h and subsequent post-sintering at 1900°C for 12 h at a nitrogen pressure of 1 MPa N₂. This thermal conductivity value is higher than that of the materials prepared from high-purity α-Si₃N₄ powder (UBE SN-E10) with the same additive composition under the same sintering conditions. In order to study the effects of Si powder characteristics on the processing, microstructure, and thermal conductivity of SRBSN, the other type of fine powder with higher native oxygen and metallic impurity (typically Al and Fe) contents was also used. The effects of Si particle size, native oxygen, and metallic impurities on the nitriding process, post-sintering process, and thermal conductivity of the resultant SRBSN materials were discussed in detail. This work demonstrates that the improvement in thermal conductivity of SRBSN could be achieved by using higher purity coarse Si powder with lower levels of oxygen and aluminum impurities. In addition, this work also shows that the nitriding temperature has no significant effect on the microstructure and thermal conductivity of SRBSN during post-sintering, although it does affect the characteristics of RBSN formed during nitridation.     

Fracture of Yttria-Doped, Sintered Reaction-Bonded Silicon Nitride

Flexural strength of an yttria-doped, slip-cast, sintered reaction-bonded silicon nitride was evaluated as a function of temperature (20° to 1400°C in air), applied stress, and time. Static oxidation at 700o to 1400°C was investigated in detail; in tests at 1000°C in air, the material showed anomalous weight gain. Flexural stress-rupture testing a 800° to 1200°C in air indicated that the material is susceptible to stress-enhanced oxidation and early failure. Fractographic evidence for time-dependent and -independent failures is presented.     

Nonaqueous Processing of Silicon for Reaction-Bonded Silicon Nitride

Ethanolic silicon suspensions, with and without a polyethoxylated amine of low molecular weight, were studied by rheological, adsorption, electrophoretic, and sedimentation methods. Pellets were pressure-cast and nitrided to form reaction-bonded silicon nitride. Density and binding strength in the green state relate well to rheological behavior and other collodial aspects of the suspensions used, particularly the additive's role and distribution. Density and degree of nitridation in the final state are not importantly affected by the additive's use. Its greatest benefit is to modify the binding strength in the green state. The mode by which this small molecule affects the processing of silicon consists of adsorption, combined with an increased electrostatic interparticle repulsion which increases the suspension viscosity and that of undried pellets. Although the improved binding strength is accompanied by decreased green and nitrided densities, high degrees of conversion to silicon nitride are still achieved.     

Nonisothermal Microwave Processing of Reaction-Bonded Silicon Nitride

The size and density of reaction-bonded silicon nitride (RBSN) specimens are limited by the reduction in pore size and pore volume associated with the nitridation reaction. In particular, under conventional heating, pores at the surface of dense compacts close before the center has reacted fully. Microwave heating offers a unique advantage over conventional heating for the processing of RBSN. A temperature gradient can be maintained within the compact, which causes the reaction to occur preferentially in the interior. This increases the amount of silicon converted to Si₃N₄ because the center of compacts with a high green density finishes reacting before the porosity near the surface closes. This study follows the reaction process and shows that partially nitrided silicon compacts have composition gradients in the radial direction. Microwave processing also facilitates control of the reaction rate.     

Sintered Reaction-Bonded Silicon Nitride with High Thermal Conductivity and High Strength

Sintered reaction-bonded silicon nitride (SRBSN) materials were prepared from a high-purity Si powder doped with Y₂O₃ and MgO as sintering additives by nitriding at 1400°C for 8 h and subsequently postsintering at 1900°C for various times ranging from 3 to 24 h. Microstructures and phase compositions of the nitrided and the sintered compacts were characterized. The SRBSN materials sintered for 3, 6, 12, and 24 h had thermal conductivities of 100, 105, 117, and 133 W/m/K, and four-point bending strengths of 843, 736, 612, and 516 MPa, respectively. Simultaneously attaining thermal conductivity and bending strength at such a high level made the SRBSN materials superior over the high-thermal conductivity silicon nitride ceramics that were prepared by sintering of Si₃N₄ powder in our previous works. This study indicates that the SRBSN route is a promising way of fabricating silicon nitride materials with both high thermal conductivity and high strength.     

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.     

Improved Aqueous Dispersion of Silicon Nitride with Aminosilanes

The addition of a standard fiberglass surfactant, 3-aminopropyltriethoxysilane (APS), improves whisker and powder dispersion of silicon nitride aqueous suspensions. Aqueous suspensions of APS-coated silicon nitride have lower viscosities, increased consolidation, and higher dried green-body densities compared to uncoated silicon nitride in suspensions with pH values ≤8. The APS coating shifts the isoelectric point (IEP) of silicon nitride to a more basic value, dependent on the concentration of APS coating. Suspension pH measurements indicate that APS extracts one hydrogen ion for each APS molecule either chemisorbed on the particle surface or dissolved in the solution. Optical microscopy reveals that dilute suspensions coated with APS at pH 10 are qualitatively more dispersed than uncoated silicon nitride at pH 7. Our results show increased dispersion of APS-coated silicon nitride in acidic environments, with a 12% increase in green density under identical wetpressing conditions.     

Reactivity of Aluminum Nitride Powder in Aqueous Silicon Nitride and Silicon Carbide Slurries

The reactivity of AlN powder with water in supernatants obtained from centrifuged Si₃N₄ and SiC slurries was studied by monitoring the pH versus time. Various Si₃N₄ and SiC powders were used, which were fabricated by different production routes and had surfaces oxidized to different degrees. The reactivity of the AlN powder in the supernatants was found to depend strongly on the concentration of dissolved silica in these slurries relative to the surface area of the AlN powder in the slurry. The hydrolysis of AlN did not occur if the concentration of dissolved silica, with respect to the AlN powder surface, was high enough (1 mg SiO₂/(m² AlN powder)) to form a layer of aluminosilicates on the AlN powder surface. This assumption was verified by measuring the pH of more concentrated (31 vol%) Si₃N₄ and SiC suspensions also including 5 wt% of AlN powder (with respect to the solids).     

Systematic Approach for Dispersion of Silicon Nitride Powder in Organic Media: II, Dispersion of the Powder

A novel dispersant—O-(2-aminopropyl)-O'-(2-methoxyethyl)-polypropylene glycol (AMPG)—was developed to disperse submicrometer-sized Si₃N₄ powder in nonaqueous media, based on the surface chemistry of the powder. The dispersing phenomena and mechanisms have been studied systematically, both in model systems (using atomic force microscopy and ellipsometry) and in powder systems (using rheological behavior and adsorption isotherms). The results from the model systems correlated well with those from wet powder systems. It is demonstrated that highly concentrated (with a solids volume fraction of >0.50) and colloidally stable nonaqueous Si₃N₄ suspensions can be realized using AMPG.     

Dynamic Fracture Toughnesses of Reaction-Bonded Silicon Nitride

Dynamic fracture toughness specimens consisting of 5.1-mm thick, modified wedge-loaded, tapered double-cantilever-beam (WL-MTDCB) specimens, which are side-grooved on one side, were used to establish the room-temperature dynamic fracture toughness, K _ID vs crack velocity, a , relations of two reaction-bonded silicon nitrides. The measured dynamic crack extension histories were then used to drive a dynamic finite-element code in its generation mode which computes the dynamic stress intensity factors for a given crack extension. Results indicate that the K _ID vs a relations of reaction-bonded silicon nitrides do not follow the general trend in those relations of brittle polymer and steel. The slow initial crack velocity which was reported for glass was observed again in silicon nitride and resulted in a nonunique K _ID vs a relation, in contrast to the unique K _ID vs a material properties reported for brittle polymers and metals.     

Thermal Oxidation of Sputter-Coated Reaction-Bonded Silicon Nitride

Ceramic coatings prepared by sputtering and reactive sputtering were applied to reaction-bonded silicon nitride surfaces to prevent extensive oxidation of the underlying material. The high-density nitride-based coatings retard the oxidation of the substrate by forming an oxygen diffusion barrier which seals the open porosity while maintaining dimensional and thermal stability. The oxidation kinetics of the coated and uncoated reaction-bonded silicon nitride substrates were compared at T = 1000 ° to 1200°C. Oxidation of the underlying material in this temperature range was substantially reduced when suitable coatings were used and the crystalline oxidation product (cristobalite) was essentially eliminated.     

氮化硅粉体的表面化学性质和水中的胶体特性

陶瓷粉体的表面性质和胶体行为对成型、烧结等工艺过程有很大影响。本文回顾了近年来对氮化硅粉体的表面化学性质和水中的胶体特性的研究成果。系统介绍了氮化硅粉体表面元素的键合状态、表面官能团、氧在颗粒表面和内部的分布和表面富氧层的厚试行表面化学性质,以及氮化硅颗粒在水中的荷电机理、等电点和Ｚｅｔａ电位与表面氧含量的关系、含烧结助剂氮化硅多相体系的胶体特性和分散剂的作用机理等胶体特性。     

Formation of Reaction-Bonded Silicon Nitride Using Microwave Heating

Rod-shaped silicon compacts were nitrided in a microwave applicator using a minimum of insulation in order to maximize the temperature gradients to effect an inside-out reaction. These specimens exhibited very nonuniform conversion to Si₃N₄, and fully nitrided areas had poor microstructures consisting of alternating regions of high and low density. The key factor was found to be sintering of the silicon powder during initial heating which caused the specimens to be electrically conducting during the early stages of the reaction and led to large changes in the microwave heating behavior of the specimens as they nitrided. The temperature and composition profiles in the specimens were simulated using a numerical model. The results of the model indicated that the observed microstructures were caused by high temperatures and temperature gradients in the areas of maximum nitridation rate which caused silicon vapor to diffuse within the specimens. Some compacts were made from a mixture of silicon powder and silicon nitride powder to avoid sintering of the silicon particles. These specimens nitrided uniformly with inside-out composition profiles, indicating that microwave heating would be beneficial for the nitridation of pure silicon powder compacts if sintering could be avoided.     

Infiltration of Reaction-Bonded Silicon Nitride with Equilibrium Y-Si-O-N Melt

An equilibrium Y-Si-O-N melt was infiltrated to eliminate the open porosity of reaction-bonded silicon nitride at 1600–1800°C. This oxynitride melt contained two equilibrium phases, a β-Si₃N₄ solid phase and a liquid phase at high temperatures. Before infiltration, porous reaction-bonded silicon nitride compacts were heat-treated to completely transform to the β-Si₃N₄ phase. After infiltration, the flexural strength of the reaction-bonded silicon nitride material increased from 200 to 600 MPa at 25°C, from 200 to 300 MPa at 1400°C in air.     

Oxidation and Fracture Strength of High-Purity Reaction-Bonded Silicon Nitride

Reaction-bonded Si₃N₄ (RBSN) made from high-purity Si powder is unusually resistant to degradation caused by exposures to air for up to 50 h at temperatures up to 1400°C. The weight gain during oxidation of this SiH₄-originating RBSN is approximately 10 times less than conventional RBSN. Contrary to normally observed strength degradations, room-temperature strengths of this high-purity, oxidized RBSN (avg = 435 MPa, max. = 668 MPa) remained at their unusually high, as-processed levels after 1000° and 1400°C oxidizing exposures. Fracture toughness values were unaffected by oxidation ( K _IC= 2.3 to 2.4 MPa · m^1/2). This superior oxidation resistance results from the high purity and the small diameter pore channels (0.01 to 0.06 μm) achieved in this SiH₄-originating RBSN.     

Microstructure of Reaction-Bonded Silicon Nitride Consolidated by Isostatic Hot-Pressing

Reaction-bonded Si₃N₄ specimens which had been isostatically hot-pressed at 1850°, 1950°, and 2050°C were examined microstructurally and by chemical analyses. Previously reported data indicated an increase in the 1200°C bend strength of reaction-bonded Si3N4 only after it was pressed at 2050°C. Observations from the present study indicate that this behavior results from the relative oxygen levels of the isostatically hot-pressed specimens. Calculations show that an Si02 content of 52.2 vol% is required to realize an increase in the 1200°C strength.     

Mechanical Properties of Sintered and Nitrided Laser-Synthesized Silicon Powder

Pure and boron-doped silicon powders made by laser-heated gas-phase synthesis were densified by pressureless sintering and then nitrided. Modulus of rupture, hardness, and fracture toughness were measured for reaction-bonded Si₃N₄ samples made from these powders and for other standard materials for comparison.     

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.     

Effect of Hot Isostatic Pressing on Reaction-Bonded Silicon Nitride

Reaction-bonded silicon nitride was isostatically hot-pressed under 138 MPa for 2 h at 1850°, 1950°, or 2050°C. Nearly theoretically dense specimens resulted. The room-temperature flexural strength more than doubled, but the 1200°C flexural strength increased significantly only after pressing at 2050°C.f. ∼35% improvement). An amorphous phase introduced by hot isostatic pressing accounts in part for these results.