Spark Plasma Sintered Silicon Nitride Ceramics with High Thermal Conductivity Using MgSiN2 as Additives

Silicon nitride ceramics were prepared by spark plasma sintering (SPS) at temperatures of 1450°–1600°C for 3–12 min, using α-Si₃N₄ powders as raw materials and MgSiN₂ as sintering additives. Almost full density of the sample was achieved after sintering at 1450°C for 6 min, while there was about 80 wt%α-Si₃N₄ phase left in the sintered material. α-Si₃N₄ was completely transformed to β-Si₃N₄ after sintering at 1500°C for 12 min. The thermal conductivity of sintered materials increased with increasing sintering temperature or holding time. Thermal conductivity of 100 W·(m·K)⁻¹ was achieved after sintering at 1600°C for 12 min. The results imply that SPS is an effective and fast method to fabricate β-Si₃N₄ ceramics with high thermal conductivity when appropriate additives are used.     

Near-Net Shape β-Si4Al2O2N6 Parts by Hydrolysis Induced Aqueous Gelcasting Process

In this paper, a new net-shaping process, an hydrolysis-induced aqueous gelcasting (GC) (GCHAS) has been reported for consolidation of β-Si₄Al₂O₂N₆ ceramics from aqueous slurries containing 48–50 vol%α-Si₃N₄, α-Al₂O₃, AlN, and Y₂O₃ powders mixture. Dense ceramics of same composition were also consolidated by aqueous GC and hydrolysis assisted solidification routes. Among three techniques used, the GCHAS process was found to be superior for fabricating defect-free thin wall β-Si₄Al₂O₂N₆ crucibles and tubes. Before use, the as purchased AlN powder was passivated against hydrolysis. The sintered β-Si₄Al₂O₂N₆ ceramics exhibited comparable properties with those reported for similar materials in the literature.     

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.     

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.     

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.     

Mechanical Property and Oxidation Behavior of Self-Reinforced Si3N4 Doped with Re2O3 (Re=Yb, Lu)

In this work, self-reinforced silicon nitrides with β-Si₃N₄ seeds doped with Re₂O₃ (Re=Yb, Lu) were investigated. Firstly, the two kinds of seeds were obtained by heating α-Si₃N₄ powder with Yb₂O₃ or Lu₂O₃, respectively. Then the self-reinforced silicon nitride ceramics were prepared by HP-sintering of α-Si₃N₄ powder, Re₂O₃ as additive, and the as-prepared seeds. Oxidation test was carried out at 1400°C in air for 100 h with thermogravimetry analysis (TGA) measurement. Mechanical properties, scanning electronic microscopy microstructures, and X-ray diffraction patterns were measured before and after oxidation. The results indicated that the introduction of the seeds doped with Re₂O₃ (Re=Yb, Lu) could obviously increase the toughness and keep the room temperature and high-temperature strength of the ceramics at high values. After oxidation, the crystalline phase in grain boundary changed and the mechanical properties decreased. TGA showed a parabolic weight gain and the oxidation mechanism was discussed.     

Combustion Synthesis of Si3N4–SiC Composite Powders

Fine Si₃N₄-SiC composite powders were synthesized in various SiC compositions to 46 vol% by nitriding combustion of silicon and carbon. The powders were composed of α-Si₃N₄, β-Si₃N₄, and β-SiC. The reaction analysis suggested that the SiC formation is assisted by the high reaction heat of Si nitridation. The sintered bodies consisted of uniformly dispersed grains of β-Si₃N₄, β-SiC, and a few Si₂N₂O.     

Residual α–Si3N4 in O' Crystals in CeO2-Doped O'+β' SiAlON Ceramics

The microstructure of a pressureless sintered (1605°C, 90 min) O'+β' SiAlON ceramic with CeO₂ doping has been investigated. It is duplex in nature, consisting of very large, slablike elongated O' grains (20–30 μm long), and a continuous matrix of small rodlike β' grains (< 1.0 μm in length). Many α-Si₃N₄ inclusions (0.1–0.5 μm in size) were found in the large O' grains. CeO₂-doping and its high doping level as well as the high Al₂O₃ concentration were thought to be the main reasons for accelerating the reaction between the α-Si₃N₄ and the Si-Al-O-N liquid to precipitate O'–SiAlON. This caused the supergrowth of O' grains. The rapid growth of O' crystals isolated the remnant α–Si₃N₄ from the reacting liquid, resulting in a delay in the α→β-Si₃N₄ transformation. The large O' grains and the α-Si₃N₄ inclusions have a pronounced effect on the strength degradation of O'+β' ceramics.     

Microstructural Observations on Hot-Pressed Si3N4

The development of microstructure in hot-pressed Si_aN₄ was studiehd for a typical Si₃N₄ powder with and without BeSiN₂ as a densification aid. The effect of hot-pressing temperature on density, α- to β-Si₃N₄ conversion and specific surface area showed that BeSiN₂ appears to increase the mobility of the system by enhancing densification, α- to β-Si₃N₄ transformation, and grain growth at temperatures between 1450° and 1800°. These processes appear to occur in the presence of a liquid phase.     

Thermal Conductivity of β-Si3N4: III, Effect of Rare-Earth (RE = La, Nd, Gd, Y, Yb, and Sc) Oxide Additives

β-Si₃N₄ ceramics sintered with a series of rare-earth (RE = La, Nd, Gd, Y, Yb and Sc) oxide additives were fabricated by hot pressing and subsequent annealing. Their microstructures, lattice oxygen contents, and thermal conductivities were evaluated. Mean grain size increased, while lattice oxygen content decreased, and hence, thermal conductivity increased with decreasing ionic radius of the rare-earth element. In all cases, a marked change was observed in the order of ionic radius from La to Nd to Gd, and a little change was observed below them. Rare-earth oxide additives significantly influenced the thermal conductivity of β-Si₃N₄, unlike in the case of AlN.     

Fabrication of Si3N4/SiC Composite by Reaction-Bonding and Gas-Pressure Sintering

Si₃N₄/SiC composite materials have been fabricated by reaction-sintering and postsintering steps. The green body containing Si metal and SiC particles was reaction-sintered at 1370°C in a flowing N₂/H₂ gas mixture. The initial reaction product was dominated by alpha-Si₃N₄. However, as the reaction processed there was a gradual increase in the proportion of β-Si₃N₄. The reaction-bonded composite consisting of alpha-Si₃N₄, β-Si₃N₄, and SiC was heat-treated again at 2000°C for 150 min under 7-MPa N₂ gas pressure. The addition of SiC enhanced the reaction-sintering process and resulted in a fine microstructure, which in turn improved fracture strength to as high as 1220 MPa. The high value in flexural strength is attributed to the formation of uniformly elongated β-Si₃N₄ grains as well as small size of the grains (length = 2 μm, thickness = 0.5 μm). The reaction mechanism of the reaction sintering and the mechanical properties of the composite are discussed in terms of the development of microstructures.     

Impurity Phases in Hot-Pressed Si3N4

Impurity phases in commercial hot-pressed Si₃N₄ were investigated using transmission electron microscopy. In addition to the dominant, β-Si₃N₄ phase, small amounts of Si₂N₂O, SiC, and WC were found. Significantly, a continuous grain-boundary phase was observed in the ∼ 25 high-angle boundaries examined. This film is ∼ 10 Å thick between, β-Si₃N₄ grains and ∼ 30 Å thick between Si₂N₂O and β-Si₃N₄ grains.     

Topotactically Oriented α-Si3N4 Cores in Sintered β-Si3N4

α-Si₃N₄ core structures within β-Si₃N₄ grains have been studied by transmission electron microscopy. The grains were dispersed in an oxynitride glass which was previously melted at 1600°C. The cores were topotactically related to the as-grown β-Si₃N₄ crystallites and are related to epitactical nucleation during heat treatment as the most probable mechanism.     

Fabrication of Hard and Strong α/β-Si3N4 Composites With MgSiN2 as Addivitives

α/β-Si₃N₄ composites with various α/β phase ratios were prepared by hot pressing at 1600°–1650°C with MgSiN₂ as sintering additives. An excellent combination of mechanical properties (Vickers indentation hardness of 23.1 GPa, fracture strength of about 1000MPa, and toughness of 6.3 MPa·m^1/2) could be obtained. Compared with conventional Si₃N₄-based ceramics, this new material has obvious advantages. It is as hard as typical in-situ-reinforced α-Sialon, but much stronger than the latter (700 MPa). It has comparable fracture strength and toughness, but is much harder than β-Si₃N₄ ceramics (16 GPa). The microstructures and mechanical properties can be tailored by choosing the additive and controlling the heating schedule.     

Combustion Synthesis of Si3N4 by Selective Reaction of Silicon with Nitrogen in Air

Silicon nitride (Si₃N₄) was synthesized by a selective combustion reaction of silicon powder with nitrogen in air. The α/β-Si₃N₄ ratio of the interior product could be tailored by adjusting the Si₃N₄-diluent content in the reactant mixtures. The synthetic β-Si₃N₄ showed a well-crystallized rod-like morphology. Mechanical activation greatly enhanced the reactivity of silicon powder, and the slow oxidation of silicon at the sample surface promoted the combustion reaction in air. The formation mechanism of Si₃N₄ was analyzed based on a proposed N₂/O₂ diffusion kinetic model, and the calculated result is in good agreement with the experimental phenomenon.     

Solvothermal Synthesis of Si3N4 Nanomaterials at a Low Temperature

Silicon nitride nanowires or nanorods have been synthesized from SiCl₄, NaN₃, and metallic Mg at temperatures ranging from 200° to 300°C. X-ray powder diffraction patterns indicated that the as-obtained products were mainly β-Si₃N₄. Scanning electron microscope and high-resolution transmission electronic microscopy showed that the samples mostly consisted of Si₃N₄ nanowires or nanorods. As metallic iron powder was used, α-Si₃N₄ was mainly formed at 250°C.     

Crystal Phase and Phonon Densities of States of β'-SiAION Ceramics, Si6-zAlzOzN8-z (0 ≤z≤ 4)

The crystal structure and phonon densities of states (DOS) of β-SiAlON ceramics, Si₆_ _z Al _z O _z N_8-z (0 < z < 4), prepared by a novel slipcast method, are studied by neutron-scattering techniques. The samples with z < 4 form a single-phase solid solution of Si-Al-O-N isostructural to β-Si₃N₄ (space group P 6 ₃/m). A consistent preferential occupation of the 2c sites by oxygen atoms and the 6 h sites by nitrogen atoms exists within this structure. The phonon DOS of β'-SiAlON displays phonon bands at ∼50 and 115 meV. These features are considerably broader than the corresponding ones in β-Si₃N₄ powder.     

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.     

Microstructure and Mechanical Properties of the in situβ-Si3N4/α'-SiAlON Composite

The in situ β-Si₃N₄/α'-SiAlON composite was studied along the Si₃N₄–Y₂O₃: 9 AlN composition line. This two phase composite was fully densified at 1780°C by hot pressing Densification curves and phase developments of the β-Si₃N₄/α'-SiAlON composite were found to vary with composition. Because of the cooperative formation of α'-Si AlON and β-Si₃N₄ during its phase development, this composite had equiaxed α'-SiAlON (∼0.2 μm) and elongated β-Si₃N₄ fine grains. The optimum mechanical properties of this two-phase composite were in the sample with 30–40%α', which had a flexural strength of 1100 MPa at 25°C 800 MPa at 1400°C in air, and a fracture toughness 6 Mpa·m^1/2. α'-SiAlON grains were equiaxed under a sintering condition at 1780°C or lower temperatures. Morphologies of the α°-SiAlON grains were affected by the sintering conditions.     

Kinetics of β-Si3N4 Grain Growth in Si3N4 Ceramics Sintered under High Nitrogen Pressure

The kinetics of anisotropic β-Si₃N₄ grain growth in silicon nitride ceramics were studied. Specimens were sintered at temperatures ranging from 1600° to 1900°C under 10 atm of nitrogen pressure for various lengths of time. The results demonstrate that the grain growth behavior of β-Si₃N₄ grains follows the empirical growth law Dⁿ– D₀ⁿ = kt , with the exponents equaling 3 and 5 for length [001] and width [210] directions, respectively. Activation energies for grain growth were 686 kJ/mol for length and 772 kJ/mol for width. These differences in growth rate constants and exponents for length and width directions are responsible for the anisotropy of β-Si₃N₄ growth during isothermal grain growth. The resultant aspect ratio of these elongated grains increases with sintering temperature and time.