Texture,microstructures, and mechanical properties of AlN‐based ceramics with Si3N4–Y2O3 additives

Textured AlN‐based ceramics with improved mechanical properties were prepared by hot pressing using Si₃N₄ and Y₂O₃ as additives. The introduction of Si₃N₄–Y₂O₃ into AlN matrix led to the formation of secondary Y₃AlSi₂O₇N₂ and fiber‐like 2H^δ AlN‐polytypoid phases, the partial texture of all crystalline phases, and the fracture mode change from intergranular to transgranular. Consequently, Vickers hardness, fracture toughness and flexural strength of AlN‐based ceramics by the replacement of Y₂O₃ by Si₃N₄–Y₂O₃ increased significantly from 10.4±0.3 GPa, 2.4±0.3 MPa m^½ and 333.3±10.3 MPa to 14.2±0.4 GPa, 3.4±0.1 MPa m^½ and 389.5±45.5 MPa, respectively.     

Influence of sintering additives on densification kinetics and high‐temperature strength in γ‐Y2Si2O7 ceramics

Pressureless sintering of pure γ‐Y₂Si₂O₇ powders that had been synthesized by a solid‐liquid reaction method using Y₂O₃ and SiO₂ powders with Li₂O, MgO, and Al₂O₃ additives was reported. The sintering kinetics of γ‐Y₂Si₂O₇ powders was analyzed to track details of densification evolution. Apparent activation energies of the densification of γ‐Y₂Si₂O₇ powders were reported for the first time, which was 57.1, 96.6, and 100.2 kJ/mol for the powders with Li₂O, MgO, and Al₂O₃ additives, respectively, indicating that Li₂O could promote the densification behavior effectively. The flexural strengths as a function of temperature for the γ‐Y₂Si₂O₇ ceramics with different additives were also investigated. The degradation of high‐temperature flexural strength was mainly ascribed to the softening of grain‐boundary glassy phase. γ‐Y₂Si₂O₇ specimens fabricated using the powders with MgO or Al₂O₃ additives exhibited better high‐temperature mechanical properties.     

常压烧结Si3N4-MgO-Y2O3-CeO2陶瓷的研究

本研究了Si3N4-MgO—Y2O3-CeO2陶瓷的烧结过程和微观结构,常压烧结氮化硅陶瓷的致密化主要通过液相烧结实现。微观分析结果表明,氮化硅烧结体的显微结构为等轴状的α—Si3N4和长柱状的β—Si3N4相互交织,这种结构有利于提高烧结体的强度和韧性。     

On the fabrication and mechanical properties of Si3N4 ceramics with low content sintering additives

Si₃N₄ ceramics were prepared by hot pressing (HP) and spark plasma sintering (SPS) methods using low content (5 mol%) Al₂O₃–RE₂O₃(RE = Y, Yb, and La)–SiO₂/TiN as sintering additives/secondary additives. The effects of sintering additives and sintering methods on the composition, microstructures, and mechanical properties (hardness and fracture toughness) were investigated. The results show that fully density Si₃N₄ ceramics could be fabricated by rational tailoring of sintering additives and sintering method, and TiN secondary additive could promote the density during HP and SPS. Besides, SN-AYS-SPS possesses the most competitive mechanical properties among all the as-prepared ceramics with the Vickers hardness as 17.31 ± .43 GPa and fracture toughness as 11.07 ± .48 MPa m^1/2.     

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.     

Silicon nitridation mechanism in reaction‐bonded Si3N4–SiC and Si3N4‐bonded ferrosilicon nitride

Reaction‐bonded Si₃N₄–SiC and Si₃N₄‐bonded ferrosilicon nitride, with Si powder, SiC particles and Fe₃Si–Si₃N₄ particles as raw materials, respectively, are prepared in flame‐isolation nitridation shuttle kiln with flowing N₂ at 1723K. There is columnar β‐Si₃N₄ in both Si₃N₄–SiC and Si₃N₄‐bonded ferrosilicon nitride. However, fibrous α‐Si₃N₄ is only observed in Si₃N₄–SiC and Si₃N₄‐bonded ferrosilicon nitride contains much more Si₂N₂O than Si₃N₄–SiC. By analyzing the oxidation thermodynamics of Si and Si₃N₄, it is known that in the process of producing Si₃N₄–SiC, Si is oxidized first to gaseous SiO and fibrous α‐Si₃N₄ is generated with SiO and N₂. The existence of SiO is the reason of low silicon nitridation rate. But in the process of producing Si₃N₄‐bonded ferrosilicon nitride, Si₃N₄ is easier to be oxidized than Si and Si₂N₂O is generated on the surface of Si₃N₄ hexagonal prisms in ferrosilicon nitride particles. Meanwhile, Si in raw materials forms new ferrosilicon alloys with Fe₃Si, which decreases the temperature of liquid appearance and blocks some open pores in the samples, which stops the matter loss of nitridation. Liquid ferrosilicon alloys favors β‐Si₃N₄ generation from Si direct nitridation and fibrous α‐Si₃N₄ transformation, which used to exist in ferrosilicon nitride raw materials.     

Synthesis of Si3N4 whiskers by rapid nitridation of silicon droplets

Belt-like β-Si₃N whiskers were successfully synthesized by nitriding of liquid silicon without catalysts at 1500°C by using micron-sized silicon powders within 10 minutes. Silicon droplets formed by the melting of silicon particles greatly facilitates the diffusion of nitrogen. Several whiskers cling together to form a whisker-cluster. The whisker-clustermorphology results from nitriding of separate silicon droplets. The growth of the belt-like β-Si₃N₄ whisker was controlled by vapor-liquid-solid mechanism. The synthesis of silicon nitride whiskers can be effectively improved by nitriding liquid phase silicon.     

Effects of Gd2O3 and MgSiN2 sintering additives on the thermal conductivity and mechanical properties of Si3N4 ceramics

Si₃N₄ ceramics were prepared by gas pressure sintering at 1900°C for 12 h under a nitrogen pressure of 1 MPa using Gd₂O₃ and MgSiN₂ as sintering additives. The effects of the Gd₂O₃/MgSiN₂ ratio on the densification, microstructure, mechanical properties, and thermal conductivity of Si₃N₄ ceramics were systematically investigated. It was found that a low Gd₂O₃/MgSiN₂ ratio facilitated the thermal diffusivity of Si₃N₄ ceramics while a high Gd₂O₃/MgSiN₂ ratio benefited the densification and mechanical properties. When the Gd₂O₃/MgSiN₂ ratio was 1:1, Si₃N₄ ceramics obtained an obvious exaggerated bimodal microstructure and the optimal properties. The thermal conductivity, flexural strength, and fracture toughness were 124 W·m⁻¹·k⁻¹, 648 MPa, and 9.12 MPa·m^1/2, respectively. Comparing with the results in the literature, it was shown that Gd₂O₃-MgSiN₂ was an effective additives system for obtaining Si₃N₄ ceramics with high thermal conductivity and superior mechanical properties.     

Microstructure evolution of Si3N4 ceramics with high thermal conductivity by using Y2O3 and MgSiN2 as sintering additives

Silicon nitride (Si₃N₄) ceramics were prepared by gas-pressure sintering using Y₂O₃–MgSiN₂ as a sintering additive. The densification behavior, phase transition, and microstructure evolution were investigated in detail, and the relevance between the microstructure and the performance (including thermal conductivity and mechanical properties) was further discussed. A significant change from a bimodal to a homogeneous microstructure and a decreased grain size occurred with increasing Y₂O₃–MgSiN₂ content. When the small quantity of preformed β-Si₃N₄ nuclei grew preferentially and rapidly in a short time, an obvious bimodal microstructure was obtained in the sample with 4 mol% and 6 mol% Y₂O₃–MgSiN₂. When more β-Si₃N₄ nuclei grew at a relatively rapid rate, the sample with 8 mol% Y₂O₃–MgSiN₂ showed a microstructure consisting of numerous abnormally grown β-Si₃N₄ grains and small grains. When more β-Si₃N₄ nuclei grew simultaneously and slowly, there was a homogeneous microstructure and smaller grains in the sample containing 10 mol% Y₂O₃–MgSiN₂. Benefitting from the completely dense, significant bimodal microstructure, low grain boundary phase, and excellent Si₃N₄–Si₃N₄ contiguity, the sample containing 6 mol% Y₂O₃–MgSiN₂ exhibited great comprehensive performance, with a maximum thermal conductivity and fracture toughness of 84.1 W/(m⋅K) and 8.97 MPa m^1/2, as well as a flexural strength of 880.2 MPa.     

Synthesis of well‐dispersed β‐Si3N4 with equiaxed structures using carbothermal reduction–nitridation method

Well‐dispersed β‐Si₃N₄ powders with a novel equiaxed structure and eminent crystal integrity were prepared by carbothermal reduction–nitridation (CRN) strategy with the assistance of CaF₂ additive. The growth mechanism of Si₃N₄ particles in the CRN process was elucidated. It is proposed that the liquid phase formed by SiO₂ and CaF₂ additive is crucial to the formation of equiaxed β‐Si₃N₄, and with an appropriate content of CaF₂, Si₃N₄ powders with pure β phase, superior dispersity and crystal integrity can be obtained.     

Electrical resistivity of Si3N4 ceramics with Yb2O3 additive

Si₃N₄ ceramics with excellent mechanical properties are used for heat dissipation substrates and so on. In order to improve their reliability and expand their application fields, it is desirable to understand and control the electrical properties of Si₃N₄ ceramics. In this study, the electrical resistivity of Si₃N₄ ceramics with Yb₂O₃ additive was investigated by applying various voltages at temperatures ranging from 25°C to 300°C. When Yb₂O₃ was added as a sintering aid to Si₃N₄ ceramics, a crystalline J-phase (Yb₄Si₂O₇N₂) was formed and their electrical resistivity was significantly lower than that of Y₂O₃ additive. The electrical resistivity of the Yb₂O₃-added ceramics decreased with an increase in temperature and applied voltage. Yb existed in multiple valence states, Yb²⁺ and Yb³⁺, in the Si₃N₄ ceramics and the decrease in the electrical resistivity can be attributed hopping conduction through the J-phase. The J-phase in the Si₃N₄ ceramics was observed to be continuous, and percolation analysis suggested that the J-phase formed an infinite cluster. Therefore, the decrease in the electrical resistivity of the Yb₂O₃-added Si₃N₄ ceramics was found mainly to result from the formation of an infinite cluster of J-phase, which exhibits hopping conduction.     

Comparison of hydrothermal corrosion behavior of SiC with Al2O3 and Al2O3 + Y2O3 sintering additives

Fully dense SiC bulks with Al₂O₃ and Al₂O₃ + Y₂O₃ sintering additives were prepared by spark plasma sintering and the effect of sintering additives on the hydrothermal corrosion behavior of SiC bulks was investigated in the static autoclave at 400°C/10.3 MPa. The SiC specimen with Al₂O₃ sintering additive exhibited a higher weight loss and followed a linear law. However, the SiC specimen with Al₂O₃ + Y₂O₃ additive exhibited a lower weight loss and followed a parabolic law, indicating that the corrosion kinetic and mechanism were different for these two SiC bulks. Further examination revealed that, a deposited layer was formed on the surface of SiC specimen with Al₂O₃ + Y₂O₃ sintering additive after corrosion, which can effectively protect the SiC specimen from further corrosion, and thereby improved the corrosion resistance of the SiC specimen with Al₂O₃ + Y₂O₃ sintering additive.     

Anisotropic properties of textured h-BN matrix ceramics prepared using 3Y2O3-5Al2O3(-4MgO) as sintering additives

Textured hexagonal boron nitride (h-BN) matrix composite ceramics were prepared by hot pressing using 3Y₂O₃-5Al₂O₃ (mole ratio of 3:5) and 3Y₂O₃-5Al₂O₃-4MgO (mole ratio of 3:5:4) as liquid phase sintering additives, respectively. During the sintering process with liquid phase environments, platelike h-BN grains were rotated to be perpendicular to the sintering pressure, forming the preferred orientation with the c-axis parallel to the sintering pressure. Both h-BN matrix ceramic specimens show significant texture microstructures and anisotropic mechanical and thermal properties. The h-BN matrix ceramics prepared with 3Y₂O₃-5Al₂O₃-4MgO possess higher texture degree and better mechanical properties. While the anisotropy of thermal conductivities of that prepared with 3Y₂O₃-5Al₂O₃ is more significant. The phase compositions and degree of grain orientation are the key factors that affect their anisotropic properties.     

Ultra-rapid microwave sintering of pure and Y2O3-doped MgAl2O4

MgAl₂O₄ samples were microwave sintered to near-full density in rapid processes with heating rates on the order of 100°C/min and zero isothermal hold. The experiments were carried out using a gyrotron system for microwave processing of materials operating at a frequency of 24 GHz with a maximum power of 6 kW. In the regimes with a preset heating rate sustained by the automatically regulated microwave power, the maximum achieved density was about 95% of the theoretical value in pristine MgAl₂O₄ samples (maximum sintering temperature 1650°C) and about 97% in 1 wt.% Y₂O₃-doped samples (1700°C). In the regimes with a fixed microwave power (about 3.5 kW), translucent spinel samples with a relative density above 99% were obtained at 1700°C. The duration of the high-temperature stage of sintering was 1.5-10 minutes. The suggested mechanism responsible for the enhanced densification involves development of a thermal instability and formation of transient liquid phases at grain boundaries. The estimated specific absorbed power in the samples during the high-temperature stage of ultra-rapid microwave sintering was 27-80 W/cm³, similar to the values observed in dc field-assisted flash sintering experiments.     

纳米Si3N4-SiC(Y2O3)复合粉末的氨解溶胶-凝胶法合成

以硅溶胶、尿素和碳黑为原料,经氨解溶胶－凝胶、碳热还原法合成了纳米Ｓｉ３ｎ４－ＳｉＣ复合粉末。通过在硅溶胶中引入Ｙ（ＮＯ３）３,合成了Ｓｉ３ｎ４－ＳｉＣ－Ｙ２Ｏ３超细复合粉末,Ｙ２Ｏ３的加入有助于降低Ｓｉ３Ｎ４－ＳｉＣ的合成温度。采用ＸＰＳ和ＸＲＤ分析复合粉末中Ｙ的存在状态表明：一部分Ｙ固溶在Ｓｉ３Ｎ４－ＳｉＣ中,加有一部分以Ｙ２Ｏ３形式存在,Ｓｉ３Ｎ４－ＳｉＣ－Ｙ２Ｏ３复合粉末的烧结性能良好。     

Effect of ZrB2 content on phase assemblage and mechanical properties of Si3N4–ZrB2 ceramics prepared at low temperature

Based on the previous work on Si₃N₄–ZrB₂ [Wu et al. J Eur Ceram Soc;2017,37:4217], the influence of ZrB₂ addition on the phase and microstructure evolution of Si₃N₄–ZrB₂ composites was emphatically investigated, and the mechanical properties were compared with pure Si₃N₄ ceramics. It was revealed that the ratio of β‐ to (α+β)‐Si₃N₄ significantly increased from 14.3% in pure Si₃N₄ ceramics to 39.8% in Si₃N₄ with 15 vol% ZrB₂ addition, indicating that the introduction of ZrB₂ promoted α‐ to β‐Si₃N₄ phase transformation. As a consequence, the microstructure of the composite showed the bimodal distribution, containing both elongated and equiaxed Si₃N₄ grains. For the pure Si₃N₄, Vickers hardness, fracture toughness and flexural strength was 22.8 GPa, 7.6 MPa m^1/2, and 334.5 MPa, respectively. In contrast, the composite of Si₃N₄–30 vol% ZrB₂ simultaneously possessed an excellent combination of mechanical properties: 19.5 GPa in hardness, 9.8 MPa m^1/2 in toughness and 702.0 MPa in strength. Present study suggested that Si₃N₄‐based ceramics with high hardness, high toughness, and high strength could be obtained by the combination of appropriate ZrB₂ content and low hot‐pressing temperature.     

Powder chemistry effects on the sintering of MgO‐doped specialty Al2O3

In this work, we investigate the effects of powder chemistry on the sintering of MgO‐doped specialty alumina. The stages at which MgO influences densification of Al₂O₃ were identified by comparing dilatometry measurements and the sintering kinetics of MgO‐free and MgO‐doped specialty alumina powders. MgO is observed to reduce the grain boundary thickness during densification using TEM. We show that MgO increases the solubility of SiO₂ in alumina grains near the boundaries using EDS. First‐principles DFT calculations demonstrate that the co‐dissolution of MgO and SiO₂ in alumina is thermodynamically favored over the dissolution of MgO or SiO₂ individually in alumina. This study experimentally demonstrates for the first time that removal of SiO₂ from the grain boundaries is a key process by which MgO enhances the sintering of alumina.     

Enhanced thermal conductivity in Si3N4 ceramic with the addition of Y2Si4N6C

Si₃N₄ ceramic was densified at 1900°C for 12 hours under 1 MPa nitrogen pressure, using MgO and self‐synthesized Y₂Si₄N₆C as sintering aids. The microstructures and thermal conductivity of as‐sintered bulk were systematically investigated, in comparison to the counterpart doped with Y₂O₃‐MgO additives. Y₂Si₄N₆C addition induced a higher nitrogen/oxygen atomic ratio in the secondary phase by introducing nitrogen and promoting the elimination of SiO₂, resulting in enlarged grains, reduced lattice oxygen content, increased Si₃N₄‐Si₃N₄ contiguity and more crystallized intergranular phase in the densified Si₃N₄ specimen. Consequently, the substitution of Y₂O₃ by Y₂Si₄N₆C led to a great increase in ~30.4% in thermal conductivity from 92 to 120 W m^?1 K^?1 for Si₃N₄ ceramic.     

逆反应烧结制备碳化硅/氮化硅复合材料的工艺

制备Si3N4／SiC复合材料的常规反应烧结是以Si和SiC为原料进行氮化烧结,而逆反应烧结是以Si3N4和SiC为原料,首先使Si3N4反向反应为活性氧化物后再进行烧结。建立逆反应烧结工艺制备Si3N4／SiC复合材料的热力学基础。确定了Si3N4先于SiC氧化;氧化产物可以是SiO2,也可以是Si2N2O;形成的SiO2氧化膜不会与基体材料反应;在膜与基体之间可能生成Si2N2O。论证了逆反应烧结的热力学可行性。通过6个烧结实验,证实了其热力学分析的正确性,并从工艺参数与密度变化、残氮率和比强度等关系筛选出最佳的烧结工艺参数。     

High quality factor microwave dielectric ceramics in the (Mg1/3Nb2/3)O2–ZrO2–TiO2 ternary system

Novel high quality factor microwave dielectric ceramics (1?x)ZrTiO₄?x(Mg_1/3Nb_2/3)TiO₄ (0.325≤x≤0.4) and (ZrTi)_1?y(Mg_1/3Nb_2/3)_yO₄ (0.2≤y≤0.5) with the addition of 0.5 wt% MnCO₃ in the (Mg_1/3Nb_2/3)O₂–ZrO₂–TiO₂ ternary system were prepared, using solid‐state reaction method. The relationship between the structure and microwave dielectric properties of the ceramics was studied. The XRD patterns of the sintered samples reveal the main phase belonged to α‐PbO₂‐type structure. Raman spectroscopy and infrared reflectivity (IR) spectra were employed to evaluate phonon modes of ceramics. The 0.65ZrTiO₄?0.35(Mg_1/3Nb_2/3)TiO₄?0.5 wt% MnCO₃ ceramic can be well densified at 1240°C for 2 hours and exhibits good microwave dielectric properties with a relative permittivity (ε_r) of 42.5, a quality factor (Q×f) value of 43 520 GHz (at 5.9 Ghz) and temperature coefficient of resonant frequency (τ_f) value of ?5ppm/°C. Furthermore, the (ZrTi)_0.7(Mg_1/3Nb_2/3)_0.3O₄?0.5 wt% MnCO₃ ceramic sintered at 1260°C for 2 hours possesses a ε_r of 31.8, a Q×f value of 35 640 GHz (at 6.3 GHz) and a near zero τ_f value of ?5.9 ppm/°C. The results demonstrated that the (Mg_1/3Nb_2/3)O₂–ZrO₂–TiO₂ ternary system with excellent properties was a promising material for microwave electronic device applications.