Na2SO4-lnduced Corrosion of Si3N4 Coated with Chemically Vapor Deposited Ta2O5

Hot isostatically pressed Si₃N₄ was coated with chemically vapor-deposited Ta₂O₅, and subjected to oxidative and corrosive environments to determine the feasibility of using a Ta₂O₅ coating for protecting Si₃N₄ from hot corrosion. The coated structure was relatively stable at 1000^deg;C in pure O₂. However, the Ta₂O₅-Si₃N₄ system became unstable in an environment containing Na₂SO₄ and O₂ at 1000^deg;C because (1) Ta₂O₅ and Na₂SO₄ reacted rapidly to form NaTaO₃ and (2) subsequently NaTaO₃ interacted destructively with the underlying Si₃N₄ substrate to form a molten phase.     

High-Temperature Chemistry and Oxidation of ZrB2 Ceramics Containing SiC, Si3N4, Ta5Si3, and TaSi2

The effect of Si₃N₄, Ta₅Si₃, and TaSi₂ additions on the oxidation behavior of ZrB₂ was characterized at 1200°–1500°C and compared with both ZrB₂ and ZrB₂/SiC. Significantly improved oxidation resistance of all Si-containing compositions relative to ZrB₂ was a result of the formation of a protective layer of borosilicate glass during exposure to the oxidizing environment. Oxidation resistance of the Si₃N₄-modified ceramics increased with increasing Si₃N₄ content and was further improved by the addition of Cr and Ta diborides. Chromium and tantalum oxides induced phase separation in the borosilicate glass, which lead to an increase in liquidus temperature and viscosity and to a decrease in oxygen diffusivity and of boria evaporation from the glass. All tantalum silicide-containing compositions demonstrated phase separation in the borosilicate glass and higher oxidation resistance than pure ZrB₂, with the effect increasing with temperature. The most oxidation-resistant ceramics contained 15 vol% Ta₅Si₃, 30 vol% TaSi₂, 35 vol% Si₃N₄, or 20 vol% Si₃N₄ with 10 mol% CrB₂. These materials exceeded the oxidation resistance of the ZrB₂/SiC ceramics below 1300°–1400°C. However, the ZrB₂/SiC ceramics showed slightly superior oxidation resistance at 1500°C.     

Synthesis and Characterization of Ti0.33Ta0.33Nb0.33C and Ti0.33Ta0.33Nb0.33CxN1-x Whiskers

Ta_0.33Ti_0.33Nb_0.33C and Ta_0.33Ti_0.33Nb_0.33C _x N_{1− x} whiskers were synthesized via a carbothermal vapor-liquid-solid growth mechanism in the temperature range 900°-1450°C in Ar or N₂. The optimum temperature was 1250°C. Whiskers were obtained in a yield of 70-90 vol%. The whiskers were 0.5–1 µm in diameter and 10–30 µm in length. The starting materials that produced the highest whisker yield were: TiO₂, Ta₂O₅, Nb₂O₅, C, Ni, and NaCl. C was added to reduce the oxides, and Ni to catalyze whisker growth. NaCl was used as a source of Cl for vapor-phase transportation of Ta and Nb oxochlorides and Ti chlorides to the catalyst. The catalyst metal was recycled several times during the synthesis and was transported as NiCl₂( g ) according to thermodynamic calculations. The rate of formation and the chemical composition of the whiskers depended on the synthesis temperature, the choice of catalyst, and the atmosphere. At low temperatures, the whiskers were enriched in Nb and Ta, whereas the Ti content increased with increased synthesis temperature.     

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.     

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.     

Reactions in the System PbO-Ta2O5

Subsolidus phase relations in the binary system PbO-Ta₂O₅ were investigated by the quenching method. The following compounds were identified by X-ray diffraction patterns: PbO -2Ta2O₅, PbO Ta₂O₆, 3PbO 2Ta₂P₅, 2PbO Ta₂O₆, 5PbO -2Ta₂O₅, and 3PbOTa₂O₅ The 1:1 compound has rhombohedral symmetry when it is prepared below 1150°C. Above this temperature, it yields an orthorhombic phase. Compounds with the same ratio of lead oxide to pentoxide exist in the systems PbO-Ta₂O₆ and PbO-Nb₂O₅.     

Phase Relations in the System CaO-Ta2O5-SiO2

The system CaO-Ta₂O₃-SiO₂ was studied using a combination of hot-stage microscopy and the quenching technique. Primary crystallization fields were defined for the various calcium silicates, and for the calcium tantalates: CaO·2Ta₂O₅, CaO·Ta₂O₅, 2CaO·Ta₂O₅, and 4CaO·Ta₂O₅. A congruently melting ternary compound 10CaO·Ta₂O₅·6SiO₂, isostructural with the mineral niocalite, is the only ternary phase in the system. A large twoliquid region extends across the system from the CaO-SiO₂ binary to within 1 wt% of the Ta₂O₃-SiO₂ binary but does not cut it, in marked contrast to the analogous CaO-Nb₂O₅-SiO₂ system. Other somewhat unexpected differences were noted between these systems.     

Effects of Temperature and Reagent Concentration on the Morphology of Chemically Vapor Deposited β-Ta2O5

Crystalline β-Ta₂O₅ coatings were deposited on hot-isostatically-pressed Si₃N₄ by reacting TaCl₅ with H₂ and CO₂ in the temperature range of 1000°–1300°C and at a pressure of 660 Pa. The Ta₂O₅ coatings generally consisted of wellcoalesced 2–3 μm grains, resulting in the formation of a nonporous coating morphology. However, the presence of microcracks on the as-deposited surface was consistently observed. The surface morphology, texture, and growth rate of the coatings were examined as a function of deposition parameters.     

Phase Equilibria in the System Si3N4-SiO2-BeO-Be3N2

The 1780°C isothermal section of the reciprocal quasiternary system Si₃N₄-SiO₂-BeO-Be₃N₂ was investigated by the X-ray analysis of hot-pressed samples. The equilibrium relations shown involve previously known compounds and 8 newly found compounds: Be₆Si³N₈, Be₁₁Si₅N₁₄, Be₅Si²N₆, Be₉Si₃N₁₀, Be₈SiO₄N₄, Be₆O₃N₂, Be₈O₅N₂, and Be₉O₆N₂. Large solid solubility occurs in β-Si₃N₄, BeSiN₂, Be₉Si₃N₁₀, Be₄SiN₄, and β-Be₃N₂. Solid solubility in β-Si₃N₄ extends toward Be₂SiO₄ and decreases with increasing temperature from 19 mol% at 1770°C to 11.5 mol% Be₂SiO₄ at 1880°C. A 4-phase isotherm, liquid +β-Si₃N₄ ( ss )Si₂ON₂+ BeO, exists at 1770°C.     

Synthesis and Luminescence Properties of Orange–Red-Emitting M2Si5N8:Eu2+ (M=Ca, Sr, Ba) Light-Emitting Diode Conversion Phosphors by a Simple Nitridation of MSi2

Eu²⁺-doped M₂Si₅N₈ (M=Ca, Sr, Ba) orange–red phosphors were successfully prepared by a simple, direct, and efficient solid-state reaction using air-stable MSi₂, Eu₂O₃, and α-Si₃N₄ as the starting materials under N₂–H₂ (5%) atmosphere. The influence of the type of the alkaline-earth ion on the phase structure and luminescence properties has been investigated. The results show that the synthesized powders have a single-phase crystal structure of M₂Si₅N₈ for M=Ca, Sr, and a little amount of BaSi₇N₁₀ impurity phase for M=Ba. Under the blue light excitation, M₂Si₅N₈:Eu²⁺ shows a typical broad band emission of Eu²⁺ ranging from orange to red (585–620 nm) depending on the type of M ion. The emission intensity, conversion efficiency, and thermal stability increase with the sequence of Ca2Si₅N₈:Eu²⁺ has the highest application potential as a red conversion phosphor for white light-emitting diodes.     

Phase Transformations in the High-Temperature Form of Pure and TiO2-Stabilized Ta2O5

The high-temperature forms of undoped tantalum pentoxide (H-100Ta₂O₅) and TiO₂–modified Ta₂O₅ (H-92Ta₂O₅–8TiO₂) were investigated by in situ synchrotron X-ray diffraction and Raman scattering measurements. Two unquenchable and reversible phase transformations were observed in pure H-Ta₂O₅, while only one was detected for TiO₂-stabilized H-Ta₂O₅. Diffraction studies were consistent with displasive transformations, but hot-stage Raman spectroscopy indicated the existence of transient intermediate forms during the transformations. Use of complementary techniques enabled the reinterpretation of phase transformations in light of a newly proposed crystal structure model for H-Ta₂O₅, ¹ and emphasized the structural contributions of the oxygen sublattice.     

Additive-Assisted Nitridation to Synthesize Si3N4 Nanomaterials at a Low Temperature

Starting from Si powder, NaN₃ and different additives such as N -aminothiourea, iodine, or both, Si₃N₄ nanomaterials were synthesized through the nitridation of silicon powder in autoclaves at 60°–190°C. As the additive was only N -aminothiourea, β-Si₃N₄ nanorods and α-Si₃N₄ nanoparticles were prepared at 170°C. If the additive was only iodine, α-Si₃N₄ dendrites with β-Si₃N₄ nanorods were obtained at 190°C. However, when both N -aminothiourea and iodine were added to the system of Si and NaN₃, the products composed of β-Si₃N₄ nanorods and α, β-Si₃N₄ nanoparticles could be prepared at 60°C.     

Formation of Metastable Fluorite Phase by Rapid Quenching of Melts in the Y2O3-Ta2O5 System

Melts of x mol% Ta₂O₅–Y₂O₃ (x = 0–32.5) were rapidly quenched to investigate the formation of metastable fluorite solid solutions. C-type Y₂O₃, fluorite, and fergusonite phases existed in the compositional regions of 0 x 16, 8 x 32.5, and 27.5 x 32.5, respectively. Their lattice parameters were precisely measured through either Rietveld analysis or a least-squares fit of the individual X-ray diffraction peak positions. The lattice parameter of the fluorite phase decreased linearly with increasing Ta₂O₅ content, strongly suggesting the formation of compositionally homogeneous metastable solid solutions. Ta₂O₅ was almost insoluble into Y₂O₃ at 1700°C in the equilibrium state.     

Nanosilver-Coated Porous SiC–Si3N4 Composite Using Microwave-Assisted Process

Using a novel microwave-assisted process, nano-Ag-coated continuous porous SiC–Si₃N₄ substrate was fabricated from a solution containing AgNO₃ salts and ethylene glycol. The detailed microstructure of the fabricated substrate was investigated depending on the amount of AgNO₃ salts in the starting solution and the microwave irradiation time. From a solution containing 0.4 g of AgNO₃ for 60 s irradiation time, the Ag nanoparticles, ∼25 nm in diameter, were homogeneously coated on the continuous porous SiC–Si₃N₄ matrix as well as on the surface of the Si₃N₄ whiskers. However, the Ag nanoparticles (∼15 nm) deposited from a solution containing 0.6 g of AgNO₃ for 60 s irradiation time showed maximum homogeneity and narrow size distribution. The components of Si, N, and Ag were homogeneously distributed on the deposited layer. The deposited Ag nanoparticles covered with a thin (∼2 nm), amorphous layer had nanocrystallinity and adhered well to the surface of the Si₃N₄ whiskers.     

XPS Investigation of Si3N4/SiC Nanocomposites Prepared Using a Commercial Polymer

We have synthesized Si₃N₄/SiC nanocomposites using a commercial polymer. Formation behavior of SiC nanoparticles has been studied using X-ray photoelectron spectroscopy (XPS). Based on the XPS results, we concluded that SiC nanoparticles were formed by a chemical reaction of Si provided from Si₃N₄ with free carbon obtained by pyrolysis of a polymer around 1300°C. The presence of CN _x compounds in samples processed in an Ar atmosphere supported our explanation.     

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.     

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.     

Mechanical Properties of Si3N4-SiC Three-Layer Composite Materials

The effects of microstructure and residual stress on the mechanical properties of Si₃N₄-based three-layer composite materials were investigated. The microstructure of each layer was controlled by the addition of two differently sized silicon carbides: fine SiC nanoparticles (∼200 nm) or relatively large SiC platelets (∼20 µm). When the SiC nanoparticles were added, the average grain size of Si₃N₄ was reduced because of the inhibition of grain growth by the particles. On the other hand, when the SiC platelets were added, the microstructure of Si₃N₄ was not much changed because of the large size of the platelets. Three-layer composites were fabricated by placing the Si₃N₄/SiC-nanoparticle layers on the surface of the Si₃N₄/SiC-platelet layer. The residual stress was controlled by varying the amount of SiC added. The mechanical properties of three-layer composites with various combinations of microstructure and residual stress level were investigated.     

Tribological Behavior of Mo5Si3-Particle-Reinforced Silicon Nitride Composites

The tribological behavior of Mo₅Si₃-particle-reinforced silicon nitride (Si₃N₄) composites was investigated by pin-on-plate wear testing under dry conditions. The friction coefficient of the Mo₅Si₃–Si₃N₄ composites and Si₃N₄ essentially decreased slowly with the sliding distance, but showed sudden increase for several times during the wear testing. The average friction coefficient of the Si₃N₄ decreased with the incorporation of submicrometer-sized Mo₅Si₃ particles and also as the content of Mo₅Si₃ particles increased. When the Mo₅Si₃–Si₃N₄ composites were oxidized at 700°C in air, solid-lubricant MoO₃ particles were generated on the surface layer. Oxidized Mo₅Si₃–Si₃N₄ composites showed self-lubricating behavior, and the average friction coefficient and wear rate of the oxidized 2.8 wt% Mo₅Si₃–Si₃N₄ composite were 0.43 and 0.72 × 10⁻⁵ mm³ (N·m)⁻¹, respectively. Both values were ∼30% lower than those for the Si₃N₄ tested in an identical manner.     

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.