Processing and Microstructural Development of In Situ TiN-Reinforced Silicon Nitride/Silicon Oxynitride Composites

The development of a novel TiN-reinforced silicon nitride/silicon oxynitride composite using an innovative in situ TiN-forming technique was investigated. Silicon powder compacts containing various amounts of TiO₂ (anatase structure) and sintering additives were nitrided under N₂ atmosphere and then further densified by hot pressing. The microstructure of the resultant composite was analyzed by X-ray diffraction, scanning electron microscopy, and solid-state nuclear magnetic resonance spectroscopy. The results of this study show that TiO₂ can be successfully converted to TiN during the nitridation of Si + TiO₂ mixture. The TiO₂ content affects not only the microstructure of the matrix but also the composition of the intergranular phase. The type and amount of sintering additives also show a significant effect on the microstructural development of the composite.     

Grain Growth Studies of Silicon Nitride Dispersed in an Oxynitride Glass

Isothermal growth of β-Si₃N₄ crystals dispersed in an oxynitride glass (Y-Si-Al-O-N) was studied by electron microscopy after heat treatment at temperatures between 1550° and 1640°C for 1 to 18 h. The β-crystals exhibited growth striations introduced by intermediate coolings and these striations were used for developing a sophisticated technique for analysis of growth. It was determined that α/β-transformation and Ostwald ripening can be treated as different kinetic stages of grain growth, while β-nucleation was found to be insignificant. The mean diameter of the needlelike β-grains was almost constant during phase transformation, indicating negligible growth of the β-prism plane; growth was mainly one-dimensional with the maximum mean length and aspect ratio just at the end of the phase transformation. The growth rate of the β-basal plane was independent of diameter, indicating interface-controlled growth. During Ostwald ripening, the length distribution broadened and the aspect ratio of smaller grains decreased. Dissolution of small grains caused an increase in the mean diameter, while the mean aspect ratio decreased.     

Fabrication of Ceramic Hip Implant Composites: Influence of Silicon Nitride on Physical,Mechanical and Wear Properties

This study examined the effects of silicon nitride reinforcement on physical, mechanical and wear properties of different ceramic (zirconium oxide, magnesium oxide, chromium oxide and aluminum oxide) containing hip implant composites. The hip implant composites were produced using conventional mixing and spark plasma sintering methods by substituting aluminum oxide (68, 70.5, 73 and 75.5 wt.%) with silicon nitride (0, 2.5, 5 and 7.5 wt.%). Experimental results showed that silicon nitride content had significant effect on the evaluated physical, mechanical and wear properties. The density of the composites found to decrease whereas void content, Young’s modulus, hardness, wear resistance and fracture toughness first decreased (for 2.5 wt.%) and then increased with the increasing amount of silicon nitride content. The maximum hardness, Young’s modulus, wear resistance and fracture toughness values of 28.64 GPa, 280.18 GPa, 0.0076 mm³/million cycles and 11.84 MPa.m^1/2, respectively were registered for 2.5 wt.% silicon nitride additions that also had the lowest void content (0.38%).

     

Mechanical Properties of Joined Silicon Nitride

A technique is described to join Si₃N₄ ceramics using oxide glasses. The technique involves a glazing step, followed by a pressureless reaction treatment of 30 to 60 min at 1575° to 1650°C. Reactions between the glasses and Si3N4 are reported. Important events are dissolution of Si₃N₄ and the growth of Si₂N₂O crystals into the joint. The strength of joined bars depends on joint thickness. Two strength regimes are identified, and two corresponding fracture mechanisms are described. A maximum strength of ∼460 MPa is achieved for a joint thickness of ∼30 μm.     

Fine-Grained Silicon Carbide Ceramics with Oxynitride Glass

By using an oxynitride glass composition from the Y-Mg-Si-Al-O-N system as a sintering additive, the effect of atmosphere on densification was investigated during the liquid-phase sintering of SiC, and the resulting microstructure and mechanical properties of the sintered and subsequently annealed materials were investigated. SiC ceramics that were densified with 10 wt% oxynitride glass showed higher sinterability in a nitrogen atmosphere. Oxynitride glass enlarged the stability region of β-SiC and suppressed β→ alpha phase transformation, which resulted in an equiaxed microstructure. Grain growth of fine-grained SiC in some extent (up to ∼300 nm) was beneficial in improving both room-temperature strength and toughness. The best results were obtained when the ceramics were hot-pressed at 1800°C for 1 h in a nitrogen atmosphere and subsequently annealed at 1900°C for 3 h in an argon atmosphere. The room-temperature flexural strength and fracture toughness of the material were 847 MPa and 3.5 MPa·m^1/2, respectively.     

Silicon Nitride/Silicon Carbide Nanocomposite Materials: I, Fabrication and Mechanical Properties at Room Temperature

The fabrication of dense Si₃N₄/SiC nanocomposite materials that contained 2.5-30 wt% SiC via gas-pressure sintering and hot pressing was investigated. The SiC particles originated from admixed commercial SiC powders, SiCN powders produced by plasma synthesis, in situ reaction pyrolysis of carbon-coated Si₃N₄ particles, and pyrolysis of a polycarbosilazane-based SiCN precursor. Based on thermodynamic calculations, criteria for minimum liquid-phase decomposition during sintering were developed. The best sintering results were obtained for sintering cycles that observed this criteria. Materials that contained plasma-synthesized SiCN exhibited high strengths (835-995 MPa) and fracture toughness values (7.4-7.8 MPam^1/2) at room temperature. Post-sintering thermal treatments led to a strength reduction.     

Fabrication and Properties of Ceramic Composites with a Boron Nitride Matrix

Boron nitride (BN) matrix composites reinforced by a number of different ceramic fibers have been prepared using a low-viscosity, borazine oligomer which converts in very high yield to a stable BN matrix when heated to 1200°C. Fibers including Nicalon (SiC), FP (A1₂O₃), Sumica and Nextel 440 (Al₂O₃-SiO₂) were evaluated. The Nicalon/BN and Sumica/BN composites displayed good flexural strengths of 380 and 420 MPa, respectively, and modulus values in both cases of 80 GPa. On the other hand, FP/BN and Nextel/BN composites exhibited very brittle behavior. Nicalon fiber with a carbon coating as a buffer barrier improved the strength by 30%, with a large amount of fiber pullout from the BN matrix. In all cases except for Nicalon, the composites showed low dielectric constant and loss.     

Fabrication and Characterization of Three-Dimensional Carbon Fiber Reinforced Silicon Carbide and Silicon Nitride Composites

Three-dimensional (3D) carbon fiber reinforced SiC and Si₃N₄ composites have been fabricated using repeated infiltration of an organosilicon slurry under vacuum and pressure. Open porosity of the infiltrated body was reduced from 40% after the first infiltration to approximately 8% after the seventh cycle. Further reduction of open porosity to less than 3% was accomplished by hot-press densification. The maximum values of flexural strength and fracture toughness were, respectively, 260 MPa and 7.3 MPa·m^1/2for C/Si₃N₄ composites, and 185 MPa and 6 MPa·m^1/2 for C/SiC composite.     

Fractography, Mechanical Properties, and Microstructure of Commercial Silicon Nitride–Titanium Nitride Composites

Commercial-grade Si₃N₄–TiN composites with 0, 10, 20, and 30 wt% TiN content have been characterized. Submicrometer grain-size Si₃N₄ was reinforced with fine TiN grains. Density, Young's modulus, coefficient of thermal expansion, and fracture toughness increased linearly with TiN content. Increased strength was observed in the Si₃N₄+20 wt% TiN, and Si₃N₄+30 wt% TiN composites. Fractography was used to characterize the different types of fracture origins. Improvements in toughness and strength are due to residual stresses in the Si₃N₄ matrix and the TiN particles. A threefold improvement in dry wear resistance of the Si₃N₄+30 wt% TiN composite over the Si₃N₄ matrix was observed.     

Design, Fabrication, and Characterization of Silicon Nitride Particle-Reinforced Silicon Nitride Matrix Composites by Chemical Vapor Infiltration

Silicon nitride particle-reinforced silicon nitride matrix composites were fabricated by chemical vapor infiltration (CVI). The particle preforms with a bimodal pore size distribution were favorable for the subsequent CVI process, which included intraagglomerate pores (0.1–4 μm) and interagglomerate pores (20–300 μm). X-ray fluorescence results showed that the main elements of the composites are Si, N, and O. The composite is composed of α-Si₃N₄, amorphous Si₃N₄, amorphous SiO₂, and a small amount of β-Si₃N₄ and free silicon. The α-Si₃N₄ transformed into β-Si₃N₄ after heat treatment at 1600°C for 2 h. The flexural strength, dielectric constant, and dielectric loss of the Si₃N_4(p)/Si₃N₄ composites increased with increasing infiltration time; however, the pore ratios decreased with increasing infiltration time. The maximum value of the flexural strength was 114.07 MPa. The dielectric constant and dielectric loss of the composites were 4.47 and 4.25 × 10⁻³, respectively. The present Si₃N_4(p)/Si₃N₄ composite is a good candidate for high-temperature radomes.     

Mechanical Properties of Hot-Pressed Silicon Nitride with Different Grain Structures

During hot-pressing of α-Si₃N₄ powders, the equiaxed α micro-structure gradually transforms into a β structure characterized by needle-shaped prismatic grains which are closely entangled and linked together. With increasing amounts of the β fraction, the bend strength, fracture toughness, and work of fracture increase significantly, then decrease as grain growth occurs. The K _lc, improves by a factor of >2 and the change in γ_F by a factor of >4. The crack resistance to achieve the same crack velocity in materials of different β contents shows a similar trend. The dependence of the mechanical properties on the microstructure is explained by linking and pullout of the β crystals and by grain coarsening.     

Silicon Nitride Oxidation Based on Oxynitride Interlayers with Graded Stoichiometry

The oxidation kinetics of Si₃N₄ were modeled by describing the simultaneous diffusion and reaction of interstitial oxygen that is believed to occur inside of the silicon oxynitride interlayer. The oxynitride was assumed to have a variable composition, and oxidation was described as a reaction where interstitial oxygen is incorporated into the network structure of the oxynitride and nitrogen is removed. It was assumed that both the diffusion coefficient and the solubility of interstitial oxygen decrease as the nitrogen content of the network structure increases. The results accurately describe both the formation of an oxynitride layer during oxidation, and the relatively slow oxidation kinetics of Si₃N₄ (compared to Si and SiC).     

Microstructure and Mechanical Properties of Silicon Nitride Ceramics with Controlled Porosity

Porous silicon nitride ceramic with a porosity from 0–0.3 was fabricated by partial hot-pressing of a powder mixture of α-Si₃N₄ and 5 wt% Yb₂O₃ as sintering additive. Irrespective of the porosity, the samples exhibited almost the same microstructural features including grain size, grain aspect ratio, and pore size. Porosity dependences of Young's modulus, flexural strength, and fracture toughness ( K _{I C} ) were investigated. All these properties decreased with increasing porosity. However, because of the fibrous microstructure, the decreases of flexural strength and fracture toughness were moderate compared with the much greater decrease of Young's modulus. Thus, the strain tolerance (fracture strength/Young's modulus) increased with increasing porosity. The critical energy release rate also increased slightly with an increasing volume fraction of porosity to 0.166 and remained at the same level with that of the dense sample when the porosity was 0.233. They decreased as porosity increased further.     

Processing, Mechanical Properties, and Oxidation Behavior of Silicon Oxynitride Ceramics

Silicon oxynitride ceramics were prepared by hot-pressing an equimolar Si₃N₄+ SiO₂ mixture with 3 mol% CeO₂. The Ce₂O₃/SiO₂ ratio of intergranular phase (liquid phase) increased as the formation of Si₂N₂O proceeded. The intergranular liquid remained as a glass on cooling until the Ce₂O₃/SiO₂ ratio exceeded a certain value, at which point the liquid crystallized. There were great differences in thermal and mechanical properties and oxideation behavior between the specimen containing intergranular glassy phase and the one containing intergranular crystalline phase (Ce₅(SiO₄)₃N–Ce_4.67(SiO₄)₃O). The specimen containing the intergranular glassy phase showed excellent hightemperature strength and oxidation resistance.     

Mechanical Properties of Three-Layered Monolithic Silicon Nitride–Fibrous Silicon Nitride/Boron Nitride Monolith

A three-layered composite, composed of a strong outer layer (monolithic S₃N₄) and a tough inner layer (fibrous Si₃N₄/BN monolith), was fabricated by hot-pressing. For the inner layer, a Si₃N₄–polymer fiber made by extrusion was coated by dipping it into a 20 wt% BN-containing slurry. The three-layered composite exhibited excellent mechanical properties, including high strength, work of fracture, and crack resistance, because of the combination of a strong outer layer and a tough inner layer. In other words, the strong outer layer withheld the applied stress, while the tough inner layer promoted crack interactions through the weak BN cell boundaries. Also, the residual thermal stress on the surface due to the anisotropy in the coefficient of thermal expansion of BN affected a median/radial crack generation after indentation.     

Silicon Nitride—Grain Boundary Oxynitride Glass Interfaces: Deductions From Glass Bulk Properties

Oxynitride glasses exist as grain boundary phases in Si₃N₄ ceramics. This paper provides an overview of oxynitride glasses outlining effects of composition on properties. A review of the effects of grain boundary glass chemistry on fracture resistance of silicon nitride is given. A knowledge of overall additive compositions and their quantities in Si₃N₄ combined with measured properties of bulk glasses allows residual stresses in the interfacial glasses to be calculated. Increase in Y:Al ratio leads to higher thermal expansion mismatch and higher residual stresses in intergranular glasses. Values are in good agreement with those obtained using micromechanical finite element analysis.     

Elevated-Temperature Mechanical Properties of Silicon Nitride/Boron Nitride Fibrous Monolithic Ceramics

A unique, all-ceramic material capable of nonbrittle fracture via crack deflection and delamination has been mechanically characterized from 25° through 1400°C. This material, fibrous monoliths, was comprised of unidirectionally aligned 250 μm diameter silicon nitride cells surrounded by 10 to 20 μm thick boron nitride cell boundaries. The average flexure strengths of fibrous monoliths were 510 and 290 MPa for specimens tested at room temperature and 1300°C, respectively. Crack deflection in the BN cell boundaries was observed at all temperatures. Characteristic flexural responses were observed at temperatures between 25° and 1400°C. Changes in the flexural response at different temperatures were attributed to changes in the physical properties of either the silicon nitride cells or boron nitride cell boundary.     

Microstructure and Mechanical Properties of Hot-Pressed Silicon Carbide-Aluminum Nitride Compositions

A flexural strength of up to 1 GPa was achieved in SiC-AIN materials and is attributed to a dense, equiaxial grain structure of the 2H(δ) SiC-AIN solid solution, with a relatively uniform grain size of ∼ 1 μm. The strength was found to decrease with increasing grain size. While the β→α phase transformation and the formation of various metastable polytypes make microstructural control difficult in SiC materials, excellent control is facilitated in SiC-AIN materials as a result of the stable 2H solid solution. Several mechanisms of grain refinement during the β→ 2H transition were observed, most notably the direct formation of several 2H grains from a single β grain. In addition, grain growth is limited by the diffusion-controlled nature of the transition. These mechanisms could be utilized to achieve even higher strength values, with potentially higher reliability of the materials in structural applications.     

纳米氮化硅陶瓷的组织与性能研究

采用热压烧结方法,以非晶纳米Si3N4和α-Si3N4粉末作为原料,制备了纳米氮化硅陶瓷,研究了起始粉末对氮化硅陶瓷组织和力学性能的影响.纳米氮化硅陶瓷的主要组成相为α-Si3N4、β-Si3N4和Si2N2O;其组织由尺寸为100nm左右的晶粒组成,α-Si3N4起始粉末的添加对组织形态没有影响.抗弯强度和断裂韧性均随α-Si3N4起始粉末含量的增加而先升后降,在其含量为40%时达到最大值;硬度随α-Si3N4粉末含量的增加而降低.