Preparation,microstructure, and properties of GPS silicon nitride ceramics with β-Si3N4 seeds and nanophase additives

Si₃N₄ ceramics with high thermal conductivity and outstanding mechanical properties were prepared by adding β-Si₃N₄ seeds and nanophase α-Si₃N₄ powders as modifiers. The introduction of β-Si₃N₄ seeds enhanced the growth of β-Si₃N₄ grains. Owing to the interlocked structure induced by the β-Si₃N₄ grains, the fracture toughness of Si₃N₄ ceramics reached a high value of 7.6 MPa·m^1/2; also, the large-sized grains increased the contact possibility of Si₃N₄ grains, improving the thermal conductivity of Si₃N₄ ceramics (64 W/(m·K)). Because of the introduction of nanophase α-Si₃N₄, the flexural strength, fracture toughness, and thermal conductivity of the Si₃N₄ ceramics increased to 754 MPa, 7.2 MPa·m^1/2, and 54 W/(m·K), respectively. According to the analysis of the growth kinetics of Si₃N₄ grains, the rapid growth of Si₃N₄ grains was ascribed to the reduction in the activation energy resulting from the introduction of β-Si₃N₄ seeds and nanophase α-Si₃N₄.     

Reaction and formation mechanism of Fe-Si3N4 composite prepared by flash combustion synthesis

In this paper, in order to improve the performance of Fe–Si₃N₄ composite synthesized by flash combustion, the detailed nitridation mechanism and formation process were discussed. In the process of high temperature nitriding, ξ phase rapidly melted to form Fe-Si melt and the cycle of rapid surface nitriding → rupture of nitridation shells → new melt exposing and nitriding occurred continually on the surface of Fe-Si melt. Since ions have different activities on the surface and internal, Fe ions near the surface migrated inwards and Si ions inside moved out; meanwhile, the Fe-Si melt kept shrinking. The nitriding reaction of the Fe-Si melt finished till the overall activity a_Si approached 0, leaving the atom ratio of [Fe] to [Si] at 3:1. During the falling of the formed Si₃N₄ and Fe₃Si melt in the N₂ flow, the surface of Si₃N₄ was oxidized to form a SiO₂ film. The nitridation product fell into the product pool, loosely stacking and adhering together by the SiO₂ film. α-Si₃N₄ dissolved and precipitated to form β-Si₃N₄ crystals, and the β-Si₃N₄ crystals kept growing to form radioactive elongated crystals. As the temperature decreased, the Fe₃Si melt cooled down; the Si-N-O melt, α-Si₃N₄ and the roots of elongated β-Si₃N₄ crystals formed the dense areas.     

Function mechanism of Y2O3 additive in silicon powder nitridation

Effect of sole Y₂O₃ additive on the nitridation behavior of silicon powder was systematically studied using thermo gravimetry, differential thermal analysis, particle size analysis, X-ray diffraction analysis, X-ray photoelectron spectroscopy, scanning electron microscope and thermodynamic analysis in this paper. The thermo gravimetry results showed that Y₂O₃ additive can significantly decrease the initial nitriding temperature and increase the nitriding rate. This phenomenon can be attributed to the much lower reaction temperature of the silica film and Y₂O₃ additive than that of the silica film and silicon. In addition, Y₂O₃ additive has little effect on the nitridation of silicon powder at 1300°C. However, it can obviously enhance the nitridation of silicon powder and the formation of β-Si₃N₄ at 1400°C, which is evidenced by the fact that the overall conversion increases from 58.1% to 100% and the fraction of β-Si₃N₄ in generated Si₃N₄ increases from 7.9% to 68.2% with increasing the content of Y₂O₃ additive from 0 to 10 wt%.     

Effect of seeding on the thermal conductivity of self-reinforced silicon nitride

Thermal conductivity of Si₃N₄ containing large β-Si₃N₄ particles as seeds for grain growth was investigated. Seeds addition promotes growth of β-Si₃N₄ grains during sintering to develop the duplex microstructure. The thermal conductivity of the material sintered at 1900 °C improved up to 106 W m⁻¹ K⁻¹, although that of unseeded material was 77 Wm⁻¹ K⁻¹. Seeds addition leads to reduction of the sintering temperature with developing the duplex microstructure and with improving the thermal conductivity, which benefits in terms of production cost of Si₃N₄ ceramics with thermal conductivity. ©     

Effect of large β-Si3N4 particles on the thermal conductivity of β-Si3N4 ceramics

Mean-field micromechanics model, the rule of mixture is applied to the prediction of the thermal conductivity of sintered β-Si₃N₄, considering that the microstructure of β-Si₃N₄ is composed of a uniform matrix phase (which contains grain boundaries and small grains of Si₃N₄) and the purified large grains (⩾2 μm in diameter) of Si₃N₄. Experimental results and theoretical calculations showed that the thermal conductivity of Si₃N₄ is controlled by the amount of the purified large grains of Si₃N₄. The present study demonstrates that the high thermal conductivity of β-Si₃N₄ can be explained by the precipitation of high purity grains of β-Si₃N₄ from liquid phase.     

Enhancement of thermal shock resistance in β-Si3N4 coating with in situ synthesized β-Si3N4 nanowires/nanobelts on porous Si3N4 ceramics

A dense β-Si₃N₄ coating toughened by β-Si₃N₄ nanowires/nanobelts was prepared by a combined technique involving chemical vapor deposition and reactive melt infiltration to protect porous Si₃N₄ ceramics in this work. A porous β-Si₃N₄ nanowires/nanobelts layer was synthesized in situ on porous Si₃N₄ ceramics by chemical vapor deposition, and then Y–Si–Al–O–N silicate liquid was infiltrated into the porous layer by reactive melt infiltration to form a dense composite coating. The coating consisted of well-dispersion β-Si₃N₄ nanowires/nanobelts, fine β-Si₃N₄ particles and small amount of silicate glass. The testing results revealed that as-prepared coating displayed a relatively high fracture toughness, which was up to 7.9 ± 0.05 MPa m^1/2, and it is of great significance to improve thermal shock resistance of the coating. After thermal cycling for 15 times at ΔT = 1200 °C, the coated porous Si₃N₄ ceramics still had a high residual strength ratio of 82.2%, and its water absorption increased only to 6.21% from 3.47%. The results will be a solid foundation for the application of the coating in long-period extreme high temperature environment.     

Influence of α-Si3N4 coarse powder on densification,microstructure, mechanical properties,and thermal behavior of silicon nitride ceramics

Silicon nitride (Si₃N₄) ceramics, with different ratios of fine and coarse α-Si₃N₄ powders, were prepared by spark plasma sintering (SPS) and heat treatment. Further, the influence of coarse α-Si₃N₄ powder on densification, microstructure, mechanical properties, and thermal behavior of Si₃N₄ ceramics was systematically investigated. Compared with fine particles, coarse particles exhibit a slower phase transition rate and remain intact until the end of SPS. The remaining large-sized grains of coarse α-Si₃N₄ induce extensive growth of neighboring β-Si₃N₄ grains and promote the development of large elongated grains. Noteworthy, an appropriate number of large elongated grains distributed among fine-grained matrix forms bimodal microstructural distribution, which is conducive to superior flexural strength. Herein, Si₃N₄ ceramics with flexural strength of 861.34 MPa and thermal conductivity of 65.76 W m⁻¹ K⁻¹ were obtained after the addition of 40 wt% coarse α-Si₃N₄ powder.     

Cost-effective manufacture and synthesis mechanism of ferrosilicon nitride porous ceramic with interlocking structure

To realize cost-effectively manufacture of high-performance Si₃N₄ porous ceramic, a ferrosilicon nitride porous ceramic with an optimized interlocking structure was synthesized by flash combustion synthesis using FeSi75 powder as raw material. And the technology has been improved in many ways to ensure stable industrial production. The theoretical combustion temperature of FeSi75 in N₂(g) is up to 4608K, while Si₃N₄ is unstable. Both adding diluent and designing the preheat temperature of nitrogen are taken to control synthesis temperature below 1600 °C. During synthesis, the Fe–Si liquid phase and SiO(g), which are essential for the selective growth of elongated columnar β-Si₃N₄ and whisker α-Si₃N₄ respectively, are formed firstly. Then, nitriding proceed in multiple ways. N diffuses through Fe–Si(l) and reacts with Si to form β-Si₃N₄, and the growth of elongated β-Si₃N₄ in Fe–Si liquid follows the dynamic ripening model, which is very fast and effective. Thus, an interlocking structure composed of elongated β-Si₃N₄ with an aspect ratio above 20 is reached. There is also an indirect nitridation reaction, that is, FeSi75 preferentially reacts with trace O₂ in atmosphere to form SiO(g), which is further nitrided to form needle-like α-Si₃N₄. Needle-like α-Si₃N₄ is interspersed in the well-developed columnar β-Si₃N₄, making the structure stronger. Fe finally exists in the form of Fe₃Si, which binds the surrounding elongated Si₃N₄ to form a sea-urchin like unit, making the structure more stable and strengthened. Through control of these reactions, optimizations in microstructure are reached, and the annual output of has reached 25,000 tons. The reaction model is established.     

Formation mechanisms of Si3N4 microstructures during silicon powder nitridation

Silicon nitride (Si₃N₄) was synthesized under a nitrogen gas flow (100 mL/min) using a molten salt nitriding method to investigate the effects of the temperature and NaCl content on the α-Si₃N₄ content in products and their micro-morphologies. Adding NaCl and β-Si₃N₄ in silicon powders resulted in Si nitridation products divided into two layers. Analysis of the lower product using X-ray diffraction revealed a change in the α-Si₃N₄ content with changes in the temperature and NaCl content. Analysis of the lower and upper layers using scanning electron microscopy revealed that the upper layer contained Si₃N₄ nanowires, Si₃N₄ nanobelts, and clastic oxide impurities; the lower one contained short needle-like and blocky Si₃N₄. From the microstructures of the products, the product morphology related to that the dry mixing procedure did not correspond to homogenization of the starting Si-Si₃N₄-NaCl mixtures and the different concentrations of raw materials resulted in different morphologies.     

A strategy for fabricating textured silicon nitride with enhanced thermal conductivity

C-axis textured Si₃N₄ with a high thermal conductivity of 176 W m⁻¹ K⁻¹ along the grain alignment direction was fabricated by slip casting raw α-Si₃N₄ powder seeded with near-equiaxed β-Si₃N₄ particles and Y₂O₃–MgSiN₂ as sintering additives in a rotating strong magnetic field of 12 T, followed by gas pressure sintering at 1900 °C for 12 h at a nitrogen pressure of 1 MPa. The green material reached a relative density of 57%, with slip casting and the sintered material exhibited a relative density of 99% and a Lotgering orientation factor of 0.98. The morphology of the β-Si₃N₄ seeds had little effect on the texture development and thermal anisotropy of textured Si₃N₄. The technique developed provides highly conductive Si₃N₄ with conductivity to the thickness direction, which is a major advantage in practical use. The technique is also simple, inexpensive and effective for producing textured Si₃N₄ with high thermal conductivity of over 170 W m⁻¹ K⁻¹.     

Nitridation behavior of silicon powder compacts of various thicknesses with Y2O3 and MgO as sintering additives

The effects of the nitriding temperature (1300 and 1350°C), holding time (0‐4 hours), and thickness of Si powder compacts on the nitridation behavior of silicon were investigated by examining the nitridation rates, analyzing phase compositions, and observing the microstructures of nitrided compacts. Si powder compacts doped with Y₂O₃ and MgO as sintering additives were prepared with thicknesses of 3, 6, and 9 mm. The phases of nitrided compacts were transformed from Si to α‐Si₃N₄ and β‐Si₃N₄ with an increase in the nitriding temperature and holding time. The degree of nitridation increased with the nitriding temperature and holding time. The β/(α+β) ratio increased with the nitriding temperature and holding time, and with a decrease in the thickness of the Si powder compacts. However, all compacts exhibited the same tendency for a higher β/(α+β) ratio at the compact surface than in the bulk of the compact. The variation in the β/(α+β) ratio for each compact decreased with an increase in the nitriding temperature and holding time.     

ZrSi2–MgO as novel additives for high thermal conductivity of β-Si3N4 ceramics

A novel ZrSi₂–MgO system was used as sintering additive for fabricating high thermal conductivity silicon nitride ceramics by gas pressure sintering at 1900°C for 12 hours. By keeping the total amount of additives at 7 mol% and adjusting the amount of ZrSi₂ in the range of 0-7 mol%, the effect of ZrSi₂ addition on sintering behaviors and thermal conductivity of silicon nitride were investigated. It was found that binary additives ZrSi₂–MgO were effective for the densification of Si₃N₄ ceramics. XRD observations demonstrated that ZrSi₂ reacted with native silica on the Si₃N₄ surface to generate ZrO₂ and β-Si₃N₄ grains. TEM and in situ dilatometry confirmed that the as formed ZrO₂ collaborated with MgO and Si₃N₄ to form Si–Zr–Mg–O–N liquid phase promoting the densification of Si₃N₄. Abnormal grain growth was promoted by in situ generated β-Si₃N₄ grains. Consequently, compared to ZrO₂-doped materials, the addition of ZrSi₂ led to enlarged grains, extremely thin grain boundary film and high contiguity of Si₃N₄–Si₃N₄ grains. Ultimately, the thermal conductivity increased by 34.6% from 84.58 to 113.91 W·(m·K)⁻¹ when ZrO₂ was substituted by ZrSi₂.     

Effect of the addition of β-Si3N4 nuclei on the thermal conductivity of β-Si3N4 ceramics

Various microstructures of β-Si₃N₄ were fabricated, with or without the addition of β-Si₃N₄ seed particles to high-purity β-Si₃N₄ powder, using Yb₂O₃ and ZrO₂ as sintering additives, by gas-pressure sintering at 1950 °C for 16 h. The thermal conductivity of the specimen without seeds was 140 W·(m·K)⁻¹, and the specimen exhibited a bimodal microstructure with abnormally grown grains. The thermal conductivity of the specimen with 24 vol.% seed addition was 143 W·(m·K)⁻¹, and this specimen had the bimodal microstructure with finer grain size than that without the seeded material, but maintained the same amount of large grains (⩾2 μm in diameter) as in the specimen without the seeds. This finding indicates that the thermal conductivity of β-Si₃N₄ is controlled by the amount of reprecipitated large grains, rather than by the grain size of the β-Si₃N₄.     

The effect of fabrication parameters on the mechanical properties of sintered reaction bonded porous Si3N4 ceramics

Porous silicon nitride ceramics were prepared via sintered reaction bonded silicon nitride at 1680 °C. The grain size of nitrided Si₃N₄ and diameter of post-sintered β-Si₃N₄ are controlled by size of raw Si. Porosity of 42.14–46.54% and flexural strength from 141 MPa to 165 MPa were obtained. During post-sintering with nano Y₂O₃ as sintering additive, nano Y₂O₃ can promote the formation of small β-Si₃N₄ nuclei, but the large amount of β-Si₃N₄ (>20%) after nitridation also works as nuclei site for precipitation, in consequence the growth of fine β-Si₃N₄ grains is restrained, the length is shortened, and the improvement on flexural strength is minimized. The effect of nano SiC on the refinement of the β-Si₃N₄ grains is notable because of the pinning effect, while the effect of nano C on the refinement of the β-Si₃N₄ grains is not remarkable due to the carbothermal reaction and increase in viscosity of the liquid phase.     

Effect of lattice impurities on the thermal conductivity of β-Si3N4

Effect of impurities in the crystal lattice and microstructure on the thermal conductivity of sintered Si₃N₄ was investigated by the use of high-purity β-Si₃N₄ powder. The sintered materials were fabricated by gas pressure sintering at 1900 °C for 8 and 48 h with addition of 8 wt.% Y₂O₃ and 1 wt.% HFO₂. A chemical analysis was performed on the loose Si₃N₄ grains taken from sintered materials after the chemical treatment. Aluminum was not removed from Si₃N₄ grains, which originated from the raw powder of Si₃N₄. The coarse grains had fewer impurities than the fine grains. Oxygen was the major impurity in the grains, and gradually decreased during grain growth. The thermal conductivity increased from 88 Wm⁻¹ K⁻¹ (8 h) to 120 Wm⁻¹ K⁻¹ (48 h) as the impurities in the crystal lattice decreased. Purification by grain growth thus improved the thermal conductivity, but changing grain boundary phases might also influence the thermal conductivity.     

Processing of biomorphic Si3N4 ceramics by CVI-R technique with SiCl4/H2/N2 system

Biomorphic porous silicon nitride Si₃N₄ ceramics have been produced by chemical vapor infiltration (CVI) of carbonized paper preforms with silicon, followed by gas–solid chemical reaction (R) of nitrogen with the infiltrated silicon. The paper was first carbonized in inert atmosphere to obtain a biocarbon (C_b) template. In a second step, silicon tetrachloride in excess of hydrogen was used to infiltrate silicon into the pores of the C_b template and to deposit silicon onto the C_b fibers. Finally, a gas–solid chemical reaction between nitrogen and infiltrated silicon in a temperature range of 1300–1450 °C took place in N₂ or N₂/H₂ atmosphere to form reaction bonded silicon nitride (RBSN) ceramics. After nitridation, the samples consist mainly of α-Si₃N₄ phase for thermal treatment below the melting point of silicon (1410 °C) or of β-Si₃N₄ phase and β-Si₃N₄/SiC-mixed ceramics for treatment at temperatures above.The crystalline phases α- and β-Si₃N₄ were identified by X-ray diffraction (XRD) analysis and the microstructure of these samples was investigated by scanning electron microscopy (SEM). Energy-dispersive X-ray analysis (EDX) was used to detect the presence of silicon, nitrogen, carbon and oxygen, whereas Raman spectroscopy was applied to identify the presence of Si and SiC. Using thermal gravimetric analysis (TGA), residual carbon was determined. It was found, that addition of 10% H₂ to the nitridation gas at temperatures near the melting point of silicon allows to increase the conversion of Si as well as to control the exothermic nitridation reaction obtaining the preferable needle-like microstructure.     

Porous Si3N4 ceramics prepared via partial nitridation and SHS

Porous Si₃N₄ ceramics were prepared via partial nitridation and self-propagating high temperature synthesis (SHS) process. Raw Si and additive Y₂O₃ were mixed and molded under 10 MPa into a compact, the compact was partial nitridation at 1300 °C to form a porous Si/Si₃N₄, and then it was buried in a Si/Si₃N₄ bed for SHS to obtain porous Si₃N₄ with rod-like β-Si₃N₄ morphology. The processing combined the advantages of the nitridation of Si and SHS with low cost, low shrinkage and time saving. Porous Si₃N₄ with a porosity of 47%, a strength of 143 MPa were obtained by this method.     

Electromagnetic wave-transparent porous silicon nitride ceramic prepared by gel-casting combined with in-situ nitridation reaction

To achieve the balance between mechanical properties and electromagnetic wave-transparent properties of porous silicon nitride (Si₃N₄), the key is to form an interlocking microstructure constituted by columnar β-Si₃N₄ crystals. This structure can be realized by liquid-phase sintering. However, grain boundaries which affect high temperature properties and volume shrinkage during sintering are inevitable. We proposed a strategy to realize this structure by gel-casting of β-Si₃N₄ whisker (Si₃N_4w) and Si powder followed by in-situ nitridation of Si. To achieve chemically-stable slurry containing micro-sized Si with low viscosity, a novel formulation was developed. Two key structural parameters of the interlocking Si₃N_4w network, i.e., density of the Si₃N_4w skeleton and inter-whisker bonding mode, were adjusted by composition of raw materials and nitridation temperature. The flexural strength, dielectric constant and loss of the porous ceramics are 44.9 MPa, 2.7 and 2 × 10⁻³, when the volume fraction of Si₃N_4w/Si is 5 and the nitriding temperature is 1400 °C.     

Preparation and characterization of porous Si3N4-bonded SiC ceramics and morphology change mechanism of Si3N4 whiskers

Porous Si₃N₄-bonded SiC ceramics with high porosity were prepared by the reaction-sintering method. In this process, Si₃N₄ was synthesized by the nitridation of silicon powder. The X-ray diffraction (XRD) indicated that the main phases of the porous Si₃N₄-bonded SiC ceramics were SiC, α-Si₃N₄, and β-Si₃N₄, respectively. The contents of β-Si₃N₄ were increased following the sintering temperature. The morphology of Si₃N₄ whiskers was investigated by scanning electron microscope (SEM), which was shown that the needle-like (low sintering-temperature) and rod-like (higher sintering-temperature) whiskers were formed, respectively. From low to high synthesized temperature, the highest porosity of the porous Si₃N₄ bonded SiC ceramic was up to 46.7%, and the bending strength was ~11.6?MPa. The α-Si₃N₄ whiskers were derived from the reaction between N₂ and Si powders, the growth mechanism was proved by Vapor–Solid (VS). Meanwhile, the growth mechanism of β-Si₃N₄ was in accordance with Vapor–Solid–Liquid (VSL) growth mechanism. With the increase of sintering temperature, Si powders were melted to liquid silicon and the α-Si₃N₄ was dissolved into the liquid then the β-Si₃N₄ was precipitated successfully.     

Synthesis and properties of AlN/MAS/Si3N4 ternary glass-ceramic composites with in-situ grown rod-like β-Si3N4 crystals

The AlN/MAS/Si₃N₄ ternary composites with in-situ grown rod-like β-Si₃N₄ were obtained by a two-step sintering process. The microstructure analysis, compositional investigation as well as properties characterization have been systematically performed. The AlN/MAS/Si₃N₄ ternary composites can be densified at 1650 °C in nitrogen atmosphere. The in-situ grown rod-like β-Si₃N₄ grains are beneficial to the improvement of thermal, mechanical, and dielectric properties. The thermal conductivity of the composites was increased from 14.85 to 28.45 W/(m K) by incorporating 25 wt% α-Si₃N₄. The microstructural characterization shows that the in-situ growth of rod-like β-Si₃N₄ crystals leads to high thermal conductivity. The AlN/MAS/Si₃N₄ ternary composite with the highest thermal conductivity shows a low relative dielectric constant of 6.2, a low dielectric loss of 0.0017, a high bending strength of 325 MPa, a high fracture toughness of 4.1 MPa m^1/2, and a low thermal expansion coefficient (α_{25–300 °C}) of 5.11 × 10^?6/K. This ternary composite with excellent comprehensive performance is expected to be used in high-performance electronic packaging materials.