Controlled Crystallization of Amorphous Si3N4by Ti and CI Additives

Thin films of amorphous Si₃N₄ were prepared by the rf-sputtering method, and the effects of titanium and chlorine additives on its crystallization were examined. When Ti-doped amorphous Si₃N₄ was heated, TiN precipitated at >1100°C; the TiN precipitates promoted the conversion of amorphous Si₃N₄ to β-Si₃N₄. Chlorine led to preferential conversion of amorphous Si₃N₄ to α-Si₃N₄.     

Controlled Crystallization in Self-Reinforced Silicon Nitride with Y2O3, SrO, and CaO: Crystallization Behavior

The controlled crystallization of the amorphous grain boundary phase has been examined in a series of self-reinforced Si₃N₄ materials with added Y₂O₃, SrO, and CaO. The effects of time, temperature, atmosphere, glass content, glass chemistry, and matrix Si₃N₄ on the crystallization have been investigated. The stability of the crystallized product, the crystallization kinetics ( T-T-T curve), and crystallization mechanisms have also been examined. Crystallization produced an oxynitroapatite containing Y, Sr, and Ca over a broad range of heat-treatment conditions and glass compositions. The oxynitroapatite was compatible with Si₃N₄ and remained stable up to 1600°C. At low temperatures (<1350°C), the rate-limiting crystallization mechanism was oxygen diffuson in the glass, and at higher temperatures (>1350°C) the rate-limiting crystallization step changed to either the formation of new Si₃N₄ grains or solute diffusion in the glass.     

Carbothermic Synthesis of Monodispersed Spherical Si3N4/SiC Nanocomposite Powder

The synthesis and structure of a monodispersed spherical Si₃N₄/SiC nanocomposite powder have been studied. The Si₃N₄/SiC nanocomposite powder was synthesized by heating under argon a spherical Si₃N₄/C powder. The spherical Si₃N₄/C powder was prepared by heating a spherical organosilica powder in a nitrogen atmosphere and was composed of a mixture of nanosized Si₃N₄ and free carbon particles. During the heat treatment at 1450°C, the Si₃N₄/C powder became a Si₃N₄/SiC composite powder and finally a SiC powder after 8 h, while retaining its spherical shape. The composition of the Si₃N₄/SiC composite powder changed with the duration of the heat treatment. The results of TEM, SEM, and selected area electron diffraction showed that the Si₃N₄/SiC composite powder was composed of homogeneously distributed nanosized Si₃N₄ and SiC particles.     

Role of Si2N2O in the Passive Oxidation of Chemically-Vapor-Deposited Si3N4

The results of two-step oxidation experiments on chemically-vapor-deposited Si₃N₄ and SiC at 1350°C show that a correlation exists between the presence of a Si₂N₂O interphase and the strong oxidation resistance of Si₃N₄. During normal oxidation, k _p for SiC was 15 times higher than that for Si₃N₄, and the oxide scale on Si₃N₄ was found by SEM and TEM to contain a prominent Si₂N₂O inner layer. However, when oxidized samples are annealed in Ar for 1.5 h at 1500°C and reoxidized at 1350°C as before, three things happen: the oxidation k _p increases over 55-fold for Si₃N₄, and 3.5-fold for SiC; the Si₃N₄ and SiC oxidize with nearly equal k _p's; and, most significant, the oxide scale on Si₃N₄ is found to be lacking an inner Si₂N₂O layer. The implications of this correlation for the competing models of Si₃N₄ oxidation are discussed.     

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.     

Long Crack R-Curve of Aligned Porous Silicon Nitride

Long crack R -curve of a porous Si₃N₄ with aligned fibrous grains was investigated, using a chevron-notched beam technique. A crack was constrained to propagate normal to the grain alignment. The crack growth resistance of aligned porous Si₃N₄ was much larger compared with that of dense Si₃N₄ ceramics. Microstructure observations showed that pullouts of fibrous grains in aligned porous Si₃N₄ markedly increased during crack propagation relative to those of dense Si₃N₄, due to the existence of pores. The efficient grain pullouts in porous Si₃N₄ increased the bridging stress at the crack wake.     

Lubricated Rolling and Sliding Wear of a SiC-Whisker-Reinforced Si3N4 Composite against M2 Tool Steel

Mineral oil lubricated rolling and sliding wear of SiC whisker (SiC_w) reinforced Si₃N₄ composite and monolithic Si₃N₄ prepared identically against M2 tool steel were investigated using a cylinder-on-cylinder apparatus. Wear of this Si₃N₄ was higher than that of the composite. Wear of the steel against Si₃N₄ was also higher than that against the composite. Relatively larger scale microfracture occurred in the Si₃N₄ than in the composite; more pullout and microchipping of carbide particles were observed in the steel against Si₃N₄ than against the composite. Polishing of the worn surfaces of the steel occurred in both sliding and rolling tests. This was attributed to fine, hard wear debris circulating in the contact area. Spalling was observed in the steel sliding against Si₃N₄ but not in the steel sliding against the composite.     

Atomistic Structure of Silicon Nitride/Silicate Glass Interfaces

The structure of interfaces formed by a Si₃N₄ grain and the silica-rich intergranular amorphous phase was investigated by quantitative high-resolution transmission electron microscopy (QHRTEM). It was found that the contrast and periodicity of the HRTEM image of β-Si₃N₄ strongly depend on the specimen thickness and objective lens focus value. The different thinning rate between Si₃N₄ and the glass phase during ion-milling results in gradients of the specimen thickness at the interfaces. The interface roughness can also lead to a thickness variation of Si₃N₄ near the interface parallel to the electron beam. As a result, the HRTEM micrographs, taken from the thin specimen regions near the interfaces at a certain defocus value, show the occurrence of an artifact of an ordered structure seemingly different from Si₃N₄. The present investigations, however, showed that no ordered phase actually different from that of Si₃N₄ at the interfacial region in Si₃N₄ could be identified so far. The interfacial structure is likely direct Si₃N₄/glass bonding, rather than an ordered transition phase between the Si₃N₄ and the glass phase.     

Molten-Salt Corrosion of Silicon Nitride: II, Sodium Sulfate

The corrosion mechanism of Si₃N₄+ Na₂SO₄/O₂ at 1000°C was investigated. Corrosion of both pure and additive-containing Si₃N₄ was studied. The reaction of Si₃N₄+ Na₂SO₄ consists of an initial period of slow weight loss due to Na₂SO₄ vaporization and oxidation-dissolution. This initial period was the same for all forms of Si₃N₄. A second region consisted of further oxidation or near termination of reaction, depending on the additive in the Si₃N₄. A 5- to 10-μm yttrium depletion zone was found after corrosion for the Si₃N₄ with yttria additives. For comparison, Si and SiC were corroded under similar conditions. These materials corroded substantially faster than all forms of Si₃N₄.     

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.     

Decomposition Suppression of Silicon Nitride by Hexagonal Boron Nitride Nanocoatings

We report a stabilized Si₃N₄ simply with nanocoatings of h-BN. Very thin BN coatings are enough for suppressing the decomposition of Si₃N₄ particles. This approach should open up a new potential way to prepare stabilized Si₃N₄. Reduced nitridation of H₃BO₃-coated Si₃N₄ powder at 1050°C in a flowing mixed 40% N₂+60% H₂ atmosphere, and then following heat-treatment at 1500°C in a flowing N₂ atmosphere can realize the nanocoating of BN on Si₃N₄ particles. Compared with the Si₃N₄ powder without nanocoatings of h-BN, TG and XRD analysis showed that the obtained h-BN nanocoated Si₃N₄ powder demonstrated obviously improved stability in argon atmosphere.     

Molten-Salt Corrosion of Silicon Nitride: I, Sodium Carbonate

Corrosion of Si₃N₄ under thin films of Na₂CO₃ was investigated at 1000°C. Pure Si₃N₄ and Si₃N₄ with various additives were examined. Thermogravimetric analysis and morphology observations lead to the following detailed reaction mechanism: (I) decomposition of Na₂CO₃ and formation of Na₂SiO₃, (II) rapid oxidation, and (III) formation of a protective silica layer below the silicate and a slowing of the reaction. For Si₃N₄ with Y₂O₃ additions, preferential attack of the grain-boundary phase occurred. The corrosion of pure Si and SiC was also studied for comparison to Si₃N₄. The corrosion mechanism generally applies to all three materials. Silicon reacted substantially faster than Si₃N₄ and SiC.     

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.     

Dissolution Kinetics of β-Si3N4 in an Mg-Si-O-N Glass

The rate of dissolution of β-Si₃N₄ into an Mg-Si-O-N glass was measured by working with a composition in the ternary system Si₃N₄-SiO₂-MgO such that Si₂N₂O rather than β-Si₃N₄ was the equilibrium phase. Dissolution was driven by the chemical reaction Si₃N₄(c)+SiO₂( l )→Si₂N₂O(c). Analysis of the kinetic data, in view of the morphology of the dissolving phase (Si₃N₄) and the precipitating phase (Si₂N₂O), led to the conclusion that the dissolution rate was controlled by reaction at the crystal/glass interface of the Si₃N₄, crystals. The process appears to have a fairly constant activation energy, equal to 621 ±40 kJ-mol⁻¹, at T=1573 to 1723 K. This large activation energy is believed to reflect the sum of two quantities: the heat of solution of β-Si₃N₄ hi the glass and the activation enthalpy for jumps of the slower-moving species across the crystal/glass interface. The data reported should be useful for interpreting creep and densification experiments with MgO-fluxed Si₃N₄.     

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.     

In Situ Synthesis and Microstructures of Tungsten Carbide-Nanoparticle-Reinforced Silicon Nitride-Matrix Composites

A W₂C-nanoparticle-reinforced Si₃N₄-matrix composite was fabricated by sintering porous Si₃N₄ that had been infiltrated with a tungsten solution. During the sintering procedure, nanometer-sized W₂C particles grew in situ from the reaction between the tungsten and carbon sources considered to originate mainly from residual binder. The W₂C particles resided in the grain-boundary junctions of the Si₃N₄, had an average diameter of ∼60 nm, and were polyhedral in shape. Because the residual carbon, which normally would obstruct sintering, reacted with the tungsten to form W₂C particles in the composite, the sinterability of the Si₃N₄ was improved, and a W₂C–Si₃N₄ composite with almost full density was obtained. The flexural strength of the W₂C–Si₃N₄ composite was 1212 MPa, ∼34% higher than that of standard sintered Si₃N₄.     

Dispersion Methods of Yttria in Silicon Nitride by Comminution

Sintering additives were incorporated into Si₃N₄ by attrition and ball milling using both Si₃N₄ and Al₂O₃ media. Dispersion of Y₂O₃ was observed by backscattered electron imaging. Attrition milling for only 15 min using an Si₃N₄ medium, was equivalent to 24 h of ball milling. Minimal contamination by the Si₃N₄ was encountered. [Key words: silicon nitride, yttria, comminution, sintering, dispersion.     

Formation of Reaction-Bonded Silicon Nitride from Silane-Derived Silicon Powders: Nucleation and Growth Mechanisms

The nucleation and growth of Si₃N₄ on silane-derived Si powders was investigated with transmission electron microscopy and FTIR spectroscopy. Thermogravimetric analysis (TGA) was also used to monitor the process through different stages of the reaction. The FTIR and TEM results provide clear evidence that the nucleation of crystalline Si₃N₄ coincides with the onset of rapid nitridation. Electron diffraction indicates that Si₃N₄ forms heteroepitaxially on the Si powder surfaces, with Si (111) || Si₃N₄(0001) and Si     || Si₃N₄     . Also, flat interfaces between the Si and Si₃N₄ (compared to the initial spherical surface of the Si powders) indicate that a significant rearrangement of the particle surface occurs during the initial stages of nitridation. The results reported here demonstrate that the rapid, low-temperature nitridation observed with silane-derived powders is possible because the Si/vapor surfaces are not covered with a continuous Si₃N₄ product layer. The measured nitridation rates are comparable to Si evaporation rates, which suggests that Si vaporization is rate limiting. This is significantly different from conventional RBSN, where nitridation is limited by solid-state diffusion through a Si₃N₄ product layer.     

Abrasive Wear Behavior of a Si3N4-MoSi2 Composite

MoSi₂ particles (20 vol%) have been added to Si₃N₄ to form ceramic matrix-intermetallic composites. Benefits associated with the addition of the MoSi₂ to Si₃N₄ include higher strength, higher fracture toughness, no loss in oxidation resistance, and lower electrical resistivity. However, because the hardness of MoSi₂ is approximately half that of Si₃N₄, a decrease in the specific wear rate of the Si₃N₄-20 vol% MoSi₂ composite is expected to result from the incorporation of the MoSi₂ into the Si₃N₄. In this U.S. Bureau of Mines and Los Alamos National Laboratory study, it is found, however, that the specific wear rate of the composite during two-body abrasion by SiC particles is equivalent in magnitude to the specific wear rate of monolithic Si₃N₄. The specific wear rates of both the Si₃N₄-20 vol% MoSi₂composites and monolithic Si₃N₄ are four to five times less than that of monolithic MoSi₂.     

Effect of Silicon Carbide Whisker and Titanium Carbide Particulate Additions on the Friction and Wear Behavior of Silicon Nitride

A Si₃N₄/TiC composite was previously demonstrated to exhibit improved wear resistance compared to a monolithic Si₃N₄ because of the formation of a lubricious oxide film containing Ti and Si at 900°C. Further improvements of the composite have been made in this study through additions of SiC whiskers and improved processing. Four materials—Si₃N₄, Si₃N₄/TiC, Si₃N₄/SiC_wh, and Si₃N₄/TiC/SiC_wh— were processed to further optimize the wear resistance of Si₃N₄ through improvements in strength, hardness, fracture toughness, and the coefficient of friction. Oscillatory pin on flat wear tests showed a decrease in the coefficient of friction from ∼0.7 (Si₃N₄) to ∼0.4 with the addition of TiC at temperatures reaching 900°C. Wear track profiles illustrated the absence of appreciable wear on the TiC-containing composites at temperatures above 700°C. Microscopic (SEM) and chemical (AES) characterization of the wear tracks is also included to deduce respective wear and lubricating mechanisms.