Phase Transition and Mechanical Property Modulation of Silicon Nitride at High Temperature and High Pressure
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摘要: 氮化硅（Si3N4）陶瓷因其独特的物理和化学特性，被认为是一种兼具高可靠性与经济性的新型结构陶瓷。然而，Si3N4具有强共价键，导致传统烧结难以使其致密化。为此，将高温高压烧结技术与MgO-Y2O3双元烧结助剂（Si3N4、MgO、Y2O3的质量比为94∶3∶3）相结合，实现了高温高压与液相协同烧结。通过设计双层对比实验组装，确保烧结温度相同，进而系统研究了双元烧结助剂对高压下Si3N4的烧结过程、相变行为、微观形貌和力学性能的影响。结果表明：MgO-Y2O3在烧结过程中形成液相，加速了α-Si3N4→β-Si3N4的转变，使Si3N4相变的起始温度从
1800 ℃降低至1650 ℃；同时，高压促进晶粒重排与烧结，成功制备出高致密的Si3N4陶瓷，其中，最优样品的维氏硬度达(24.5±1.9) GPa。研究工作为优化Si3N4陶瓷烧结工艺提供了新的有效策略。Abstract: Silicon nitride (Si3N4) ceramics are a novel category of structural ceramics, exhibiting both high reliability and economy value due to their unique physical and chemical properties. However, their strong covalent bonds make densification challenging, and phase transition control remains an issue. In this study, high temperature and high pressure (HTHP) sintering was utilized in combination with MgO-Y2O3 binary additives (mass ratio Si3N4∶MgO∶Y2O3 = 94∶3∶3) to achieve a synergistic sintering process involving both high pressure and liquid-phase formation. The effects of binary sintering additives on the sintering process, phase transition behavior, microscopic morphology and mechanical properties of Si3N4 under high pressure were systematically investigated by designing a two-layer comparative experimental assembly to ensure the same sintering temperature. The results show that the MgO-Y2O3 promotes the α→β phase transformation of Si3N4 through liquid phase formation, which reduces the phase transition onset temperature from1800 ℃ to1650 ℃. Furthermore, high pressure enhances grain rearrangement and densification. As a result, highly dense Si3N4 ceramics with an optimal Vickers hardness up to (24.5±1.9) GPa were successfully synthesized. These findings provide an effective strategy for preparing high-performance Si3N4 ceramics and hold significant implications for advancements in physics and material science. -
图 1 实验装置(a)、组装结构示意图(b)、温压控制曲线(c)以及烧结样品实物(d)
Figure 1. Experimental setup (a), schematic diagram of the assembly structure (b), temperature and pressure control curves (c) and optical photograph of the sintered sample (d)
图 2 Si3N4（SN）和Si3N4-MgO-Y2O3（SNMY）样品的XRD谱
Figure 2. XRD spectra of Si3N4 (SN) and Si3N4-MgO-Y2O3 (SNMY) samples
图 3 不同温度下Si3N4（SN）与Si3N4-MgO-Y2O3（SNMY）样品的体积密度对比
Figure 3. Comparison of bulk density of Si3N4 (SN) and Si3N4-MgO-Y2O3 (SNMY) samples at different temperatures
图 4 Si3N4（SN）与Si3N4-MgO-Y2O3（SNMY）样品的维氏硬度对比
Figure 4. Comparison of Vickers hardness of Si3N4 (SN) and Si3N4-MgO-Y2O3 (SNMY) samples
图 5 不同温度下Si3N4（SN）样品断裂面的SEM图像
Figure 5. SEM images of fracture surfaces of Si3N4 (SN) samples sintered at different temperatures
图 6 不同温度下Si3N4-MgO-Y2O3（SNMY）样品断裂面的SEM图像
Figure 6. SEM images of fracture surfaces of Si3N4-MgO-Y2O3 (SNMY) samples sintered at different temperatures
图 7 SNYM-
1650 ℃样品抛光表面的SEM图像及相应的EDS图谱Figure 7. SEM images and corresponding EDS patterns of the polished surfaces of the SNYM-
1650 ℃ sample
图 8 高致密Si3N4陶瓷在HTHP烧结过程中的致密化机理示意图
Figure 8. Schematic diagram of densification mechanism of highly dense Si3N4 ceramics during HTHP sintering process
表 1 不同温度下Si3N4（SN）和Si3N4-MgO-Y2O3（SNMY）样品中β-Si3N4的质量分数
Table 1. Mass fractions of β-Si3N4 in Si3N4 (SN) and Si3N4-MgO-Y2O3 (SNMY) samples under different temperatures
SN samples $w_{\beta \text{-}{\mathrm{Si_3N_4}}} $/% SNMY samples $w_{\beta \text{-}{\mathrm{Si_3N_4}}} $/% SN- 1000 ℃16.8 SNMY- 1000 ℃22.2 SN- 1200 ℃16.9 SNMY- 1200 ℃23.0 SN- 1400 ℃20.0 SNMY- 1400 ℃23.2 SN- 1600 ℃21.2 SNMY- 1600 ℃19.8 SN- 1650 ℃18.6 SNMY- 1650 ℃29.4 SN- 1700 ℃20.3 SNMY- 1700 ℃30.7 SN- 1750 ℃21.7 SNMY- 1750 ℃67.0 SN- 1800 ℃21.2 SNMY- 1800 ℃74.3 SN- 1900 ℃96.3 SNMY- 1900 ℃81.5 SN- 2100 ℃96.3 SNMY- 2100 ℃82.5 
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