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.     

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。     

Synthesis and growth mechanism of single crystal β‐Si3N4 particles with a quasi‐spherical morphology

Single‐crystal β‐Si₃N₄ particles with a quasi‐spherical morphology were synthesized via an efficient carbothermal reduction‐nitridation (CRN) strategy. The β‐Si₃N₄ particles synthesized under an N₂ pressure of 0.3 MPa, at 1450°C and with 10 mol% unique CaF₂ additives showed good dispersity and an average size of about 650 nm. X‐ray photoelectron spectroscopy analysis revealed that there was no SiC or Si–C–N compounds in the β‐Si₃N₄ products. Selected‐area electron‐diffraction pattern and high‐resolution image indicated single crystalline structure of the typical β‐Si₃N₄ particles without an obvious amorphous oxidation layer on the surface. The growth mechanism of the quasi‐spherical β‐Si₃N₄ particles was proposed based on the transmission electron microscopy and energy dispersive X‐ray spectroscopy characterization, which was helpful for controllable synthesis of β‐Si₃N₄ particles by CRN method. Owing to the quasi‐spherical morphology, good dispersity, high purity, and single‐crystal structure, the submicro‐sized β‐Si₃N₄ particles were promising fillers for preparing resin‐based composites with high thermal conductivity.     

多孔Si3N4/BN复相陶瓷的常压烧结制备

以微米级Si3N4和h-BN粉末为原料,Yb2O3-Al2O3-Y2O3为烧结助剂,采用常压烧结工艺制备了BN体积含量为25%的多孔Si3N4/25%h-BN复相陶瓷。研究了Yb2O3添加量对Si3N4/25%BN复相陶瓷力学性能的影响,通过X射线衍射和扫描电子显微镜分析了复相陶瓷的物相组成和显微结构。结果表明:随着Yb2O3添加量增加,制备的Si3N4/25%BN复相陶瓷的气孔率逐渐增大,收缩率变小,相对密度减小。Yb2O3添加量为2%(质量分数)时,Si3N4/25%BN复相陶瓷的气孔率为15.1%,相对密度为72.8%;当Yb2O3添加量提高至15%时复相陶瓷的气孔率增加至32.1%,相对密度则降至60.3%。同时随着Yb2O3添加量增加,复相陶瓷的室温抗弯强度先增大后减小,Yb2O3含量为4%时,室温抗弯强度呈现最大值,可达264.3MPa。     

Effect of Additives on the Pressureless Sintering of Aluminum Nitride between 1500° and 1800°C

Combined oxide additives (Y₂O₃, CaO, La₂O₃, CeO₂, SiO₂, TiO₂, and Fe₂O₃) were investigated as AIN sintering aids. AIN can be fully sintered at 1600°C to substantial thermal conductivity (92 W/(m·K)) using a multiple sintering aid of Y₂O₃, CaO, SiO₂, La₂O₃, and CeO₂. This lowtemperature material has small grain size (1 to 3 μm).     

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.     

氟化钙对常压烧结Si3N4/BN复相陶瓷结构与性能的影响

以微米级Si3N4和h-BN粉末为原料,CaF2–Al2O3–Y2O3为烧结助剂,采用常压烧结工艺制备了BN体积含量为25%的Si3N4/BN复相陶瓷。研究了CaF2添加量对Si3N4/BN复相陶瓷材料力学性能的影响,并通过X射线衍射和场发射扫描电镜分析了复相陶瓷的物相组成和显微组织。结果表明：随着CaF2添加量增加,制备的Si3N4/BN复相陶瓷材料气孔率逐渐增大,收缩率变小,相对密度减小。添加量为2%（质量分数）时,Si3N4/BN复相陶瓷的室温抗弯强度达145.5MPa。添加适量的CaF2可在Si3N4/BN复相陶瓷材料常压烧结过程中较大程度地破坏h-BN的卡片房式结构,将微米级的h-BN颗粒变成纳米级颗粒。     

Effects of initial α-phase content on properties of pressureless solid-state sintered SiC ceramics

α- and β-SiC starting powders of similar particle sizes were used to investigate the effect of initial α-phase content on the electrical, thermal, and mechanical properties of pressureless solid-state sintered (PSS) SiC ceramics with B₄C and C additives. For β-SiC starting powders, a coarse-grained microstructure with elongated platelet grains was formed by the transformation of 3C to 6H and finally to 4H-SiC phase. In contrast, materials prepared from α-SiC powders exhibited a fine-grained microstructure with platelet grains. This study revealed the beneficial effect of α-SiC starting powders in achieving low electrical resistivity and high thermal conductivity in PSS SiC ceramics, which was attributable to their higher sinterability, lower impurity content, and lower 6H to 4H-SiC phase transformation rate compared with β-SiC powders. The electrical resistivity decreased by an order of magnitude and the thermal conductivity increased by 32% with an increase in initial α-phase content from 0 to 100%. The flexural strength increased by approximately 16% with increasing initial α-phase content due to a decreased flaw size with decreasing grain size. However, the fracture toughness and hardness were insensitive to the change in initial α-phase content.     

Influence of Yttria–Alumina Content on Sintering Behavior and Microstructure of Silicon Nitride Ceramics

The present study investigates the influence of the content of Y₂O₃–Al₂O₃ sintering additive on the sintering behavior and microstructure of Si₃N₄ ceramics. The Y₂O₃:Al₂O₃ ratio was fixed at 5:2, and sintering was conducted at temperatures of 1300°–1900°C. Increased sintering-additive content enhanced densification via particle rearrangement; however, phase transformation and grain growth were unaffected by additive content. After phase transformation was almost complete, a substantial decrease in density was identified, which resulted from the impingement of rodlike β-Si₃N₄ grain growth. Phase transformation and grain growth were concluded to occur through a solution–reprecipitation mechanism that was controlled by the interfacial reaction.     

低温无压烧结氮化硅陶瓷的相变及致密化研究

采用氧化铝（Al2 O3）和氧化钇（Y2 O3）为烧结助剂,利用无压烧结工艺在低温下制备氮化硅陶瓷材料。利用XRD和SEM等着重研究了无压烧结氮化硅陶瓷低温阶段时的物相组成及其致密化。结果表明：当添加剂含量为10％,烧结温度高于1430℃时,α→β相转变较快;当烧结温度达到1510℃时,α相全部转变为β相。     

碳热还原-常压烧结法制备多孔氮化硅陶瓷

采用SiO2和α-Si3N4在氮气中通过碳热还原-常压反应烧结法,原位反应制备了氮化硅多孔陶瓷.由于反应中存在大量的质量损失,烧结的制品为高气孔的材料.通过改变原料中α-Si3N4与SiO2和C粉的相对含量,可以形成具有细小针状结构的β-Si3N4晶粒,以此获得气孔率可控的高性能的多孔氮化硅材料.随着原料中α-Si3N4含量的增大,烧结后,样品的总质量损失逐渐减小,收缩率逐渐降低,气孔率逐渐减小,弯曲强度逐渐增大.当α-Si3N4的质量分数为50%时,碳热还原-常压反应烧结的样品中的β-Si3N4晶粒具有更高的长径比,样品气孔率为68.7%,具有优良的力学性能,弯曲强度达到37.7MPa.     

MgSiN2 Addition as a Means of Increasing the Thermal Conductivity of β-Silicon Nitride

Si₃N₄ powders with the concurrent addition of Yb₂O₃ and MgSiN₂ were sintered at 1900°C for 2–48 h under 0.9 MPa nitrogen pressure. Microstructure, lattice oxygen content, and thermal conductivity of the sintered specimens were evaluated and compared with Si₃N₄, Yb₂O₃, and MgO addition. MgSiN₂ addition was effective for improving the thermal conductivity of Si₃N₄ ceramics, and a material with high thermal conductivity over 140 W·(m·K)⁻¹ could be obtained. For both specimens, lattice oxygen content was decreased with sintering time. However, the thermal conductivity of the MgSiN₂-doped specimen was slightly higher than the MgO-doped specimen with the same oxygen content.     

Improved thermal conductivity of β-Si3N4 ceramics by lowering SiO2/Y2O3 ratio using YH2 as sintering additive

A two-step sintering process was conducted to produce β-Si₃N₄ ceramics with high thermal conductivity. During the first step, native SiO₂ was eliminated, and Y₂O₃ was in situ generated by a metal hydride reduction process, resulting in a high Y₂O₃/SiO₂ ratio. The substitution YH₂ for Y₂O₃ endow Si₃N₄ ceramics with an increase of 29% in thermal conductivity from 95.3 to 123 W m⁻¹ K⁻¹ after sintered at 1900°C for 12 hours despite an inferior sinterability. This was primarily attributed to the purified enlarged grains, devitrified grain boundary phase, and reduced lattice oxygen content in the YH₂-MgO-doped material.     

Y2O3—Al2O3—SiO2添加剂在低温烧结SiC中的作用

本文探讨了Ｙ２Ｏ３－Ａｌ２Ｏ３添加剂在低温无压烧结ＳｉＣ中的作用以及在Ｙ２Ｏ３－Ａｌ２Ｏ３添加剂中引入ＳｉＯ２的作用及机理,从而阐明了通过多项合理、有效复合添加降低ＳｉＣ烧结温度的可能性。     

不同烧结助剂制备的Si3N4陶瓷的氧化行为

以α-Si3N4粉末为原料,分别以Y2O3-La2O3和Y2O3-CeO2为烧结助剂,利用热压烧结法制备了Si3N4陶瓷。研究了Si3N4陶瓷样品在空气中高温下的氧化行为。结果表明:原始的α-Si3N4在烧结过程中完全转化为β-Si3N4。在1000～1350℃氧化100h后,用Y2O3-La2O3烧结助剂制备的样品表现为质量增加趋势,质量变化小于0.389mg/cm2,其氧化过程符合抛物线规律。用Y2O3-CeO2烧结助剂制备的样品,在1000℃氧化后表现为质量减小,为-0.248mg/cm2;在1230℃和1350℃表现为质量增加,分别为0.024mg/cm2和0.219mg/cm2,并且其氧化过程不符合抛物线规律。样品的氧化过程主要受2个扩散过程的控制,即稀土元素的向外扩散与氧的向内扩散。     

无压烧结高导热AlN陶瓷的研究进展

AlN以其优异的高热导率、与Si相匹配的热膨胀系数及其它优良的物理化学性能受到了国内外学术界的广泛关注,被誉为新一代高密度封装的首选基板材料.本文详细综述了AlN陶瓷的导热机理和无压烧结工艺等方面的研究进展,并介绍了烧结助剂的选取原则和AlN陶瓷热导率与温度的关系,以及展望了AlN基板的发展趋势和前景.