Preparation and mechanical properties of Si3N4 nanocomposites reinforced by Si3N4@rGO particles

A new type of reduced graphene oxide-encapsulated silicon nitride (Si₃N₄@rGO) particle was synthesized via an electrostatic interaction between amino-functionalized Si₃N₄ particles and graphene oxide (GO). Subsequently, the Si₃N₄@rGO particles were incorporated into a Si₃N₄ matrix as a reinforcing phase to prepare nanocomposites, and their influence on the microstructure and mechanical properties of the Si₃N₄ ceramics was investigated in detail. The microstructure analysis showed that the rGO sheets were uniformly distributed throughout the matrix and firmly bonded to the Si₃N₄ grains to form a three-dimensional carbon network structure. This unique structure effectively increased the contact area and load transfer efficiency between the rGO sheets and the matrix, which in turn had a significant impact on the mechanical properties of the nanocomposites. The results showed that the nanocomposites with 2.25 wt.% rGO sheets exhibited mechanical properties that were superior to monolithic Si₃N₄; the flexural strength increased by 83.5% and reached a maximum value of 1116.4 MPa, and the fracture toughness increased by 67.7% to 10.35 MPa·m^1/2.     

Stress distribution around Fe5Si3 and its effect on interface status and mechanical properties of Si3N4 ceramics

Si₃N₄ ceramics with different amount of Fe₅Si₃ were prepared by adding FeSi₂. Residual thermal stress distribution and elastic energy around Fe₅Si₃ particles in various depths were calculated. The interface status between second phase particles and matrix was analyzed in terms of stress and energy. High tangential compressive stresses and low radial tensile stresses were generated along the surface of the ceramics. Elastic strain energy caused by unit interface was high around big particles in deep area of the ceramics. Microcracks are observed around the big Fe₅Si₃ particles. Furthermore, accord to our calculation, microcracks are easily generated around particles in superficial layer of matrix when second phase particles have lower thermal expansion coefficient than the matrix, while microcracks tend to be generated in deep layer of matrix preferentially when the thermal expansion coefficient of second phase particles is higher than matrix. Residual stresses and microcracks around Fe₅Si₃ particles greatly influenced mechanical properties. Fracture toughness of Si₃N₄ ceramics with similar Si₃N₄ particle size distribution increased with the amount of Fe₅Si₃, and fine Fe₅Si₃ particles could enhance the strength of Si₃N₄ ceramics. Si₃N₄ ceramics exceeding 1.2 GPa strength were prepared.     

Effect of a new nonoxide additive,Y3Si2C2, on the thermal conductivity and mechanical properties of Si3N4 ceramics

Enhancement of the thermal conductivity of silicon nitride is usually achieved by sacrificing its mechanical properties (bending strength). In this study, β-Si₃N₄ ceramics were prepared using self-synthesized Y₃Si₂C₂ and MgO as sintering additives. It was found that the thermal conductivity of the Si₃N₄ ceramics was remarkably improved without sacrificing their mechanical properties. The microstructure and properties of the Si₃N₄ ceramics were analyzed and compared with those of the Y₂O₃-MgO additives. The addition of Y₃Si₂C₂ eliminated the inherent SiO₂ and introduced nitrogen to increase the N/O ratio of the grain-boundary phase, inducing Si₃N₄ grain growth, increasing Si₃N₄ grain contiguity, and reducing lattice oxygen content in Si₃N₄. Therefore, by replacing Y₂O₃ with Y₃Si₂C₂, the thermal conductivity of the Si₃N₄ ceramics was significantly increased by 31.5% from 85 to 111.8Wm⁻¹K⁻¹, but the bending strength only slightly decreased from 704 ± 63MPa to 669 ± 33MPa.     

Microstructure and Short-Term Oxidation of Hot-Pressed Si3N4/ZrO2(+Y2O3) Ceramics

Composite ceramic materials based on Si₃N₄ and ZrO₂ stabilized by 3 mol% Y₂O₃ have been formed using aluminum isopropoxide as a precursor for the Al₂O₃ sintering aid. Densification was carred out by hot-pressing at temperatures in the range 1650° to 1800°C, and the resulting micro-structures were related to mechanical properties as well as to oxidation behavior at 1200°C. Densification at the higher temperatures resulted in a fibrous morphology of the Si₃N₄ matrix with consequent high room-temperature toughness and strength. Decomposition of the ZrO₂ grains below the oxidized surface during oxidation introduced radial stresses in the subscalar region, and from the oxidation experiments it is suggested that the ZrO₂ incorporated some N during densification.     

In situ synthesis of cobalt silicide particle reinforcing and coloring Si3N4 ceramics

In this paper, silicon nitride (Si₃N₄) ceramics with black color and high toughness were fabricated by gas pressure sintering and characterized by X-ray diffraction, Raman, scanning electron microscopy, EDS, and transmission electron microscopy. The in situ formed cobalt silicide was confirmed to contribute to the black color through the introduction of CoO. Due to the addition of CoO, the growth of β-Si₃N₄ grains is promoted, forming elongated grains, and eventually forms the self-reinforcing microstructure. However, with adding excessive CoO, interfacial debonding is found between cobalt silicide and Si₃N₄ matrix and a decrease in strength was resulted. The optimum composition is 1 mol% CoO in Si₃N₄, with the fracture toughness of 9.9 ± 0.3 MPa m^1/2, flexural strength of 826.1 ± 46.0 MPa, and a much darker black color. The mechanism of color formation is discussed where the black color derives mainly from the metallic silicon and additionally the porosity.     

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.     

Temperature-driven wear behavior of Si3N4-based ceramic reinforced by in situ formed TiC0.3N0.7 particles

Si₃N₄ as a structural ceramic is desirable for applications in spacecraft, transportation, and energy, but its poor high-temperature properties still do not satisfy the actual requirements. Here, a TiC_0.3N_0.7 reinforced Si₃N₄ ceramic is successfully designed and fabricated via the high-temperature nitridation of TiC_x. It is found that TiC_0.3N_0.7 grains with the size of 1-2 μm are uniformly dispersed in the Si₃N₄ matrix and show a firm bond with substrate. Compared with pure Si₃N₄, the doping of harder TiCN phase can effectively improve ceramic's hardness and fracture toughness at a certain temperature. Importantly, the ceramic material displays extraordinary wear resistance across a wide temperature range (eg, the wear rate of TiC_0.3N_0.7 containing Si₃N₄ over 63 times and 178 times better than pure Si₃N₄ at 600 and 900°C, respectively). More broadly, a correlation between wear mechanism and temperature is established, and the result shows that the mechanical strength and tribochemical oxidation as two key factors determine the wear behavior of the material. These results developed here can provide a springboard for preparation and optimization of multiphase ceramics that serve under high-temperature conditions.     

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.     

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.     

Effect of Oxidation on Mechanical Properties of Fibrous Monolith Si3N4/BN at Elevated Temperatures in Air

The oxidation behavior and its effect on the mechanical properties of fibrous monolith Si₃N₄/BN after exposure to air at temperatures ranging from 1000° to 1400°C for up to 20 h were investigated. After exposure at 1000°C, only the BN cell boundary was oxidized, forming a B₂O₃ liquid phase. With increasing exposure temperature, the Si₃N₄ cells began to oxidize, forming crystalline Y₂Si₂O₇, SiO₂, and silicate glass. However, in this case, a weight loss was observed due to extensive vaporization of the B₂O₃ liquid. After exposure at 1400°C, large Y₂Si₂O₇ crystals with a glassy phase formed near the BN cell boundaries. The oxidation behavior significantly affected the mechanical properties of the fibrous monolith. The flexural strength and work-of-fracture decreased with increasing exposure temperature, while the noncatastrophic failure was maintained.     

Si3N4对硫系玻璃的热学和力学性质的影响

对在两个硫系玻璃系统中引入Si3N4所产生的效应进行了研究,发现其影响程度与基玻璃的组成有关。用描述共价键固体交连程度的系统平均配位数概念讨论了这种关系。发现与处于富硫族元素组成区的硫系玻璃相比,在处于富阳性元素组成区的硫系玻璃中引入Si3N4对玻璃热、力学性能的改善程度较低。这是因为没有足够的硫族元素起连接作用,多余的Si并不能对网络交连程度的提高做贡献。进一步的研究结果证实了在不同组成区引入Si3N4对玻璃转变温度θg的不同影响。在富阳性元素组成区θg甚至随系统平均配位数的增加而略有提高的原因则在于“错键效应”对玻璃网络所可能起到的局部连接作用。     

Si3N4/Si3N4扩散连接的力学性能研究

采用热压法进行氮化硅陶瓷材料的扩散连接.结果表明:在1520℃,15MPa,60min条件下,氮化硅连接体的最高强度为448.6MPa,超过母材强度;平均连接强度为401.5MPa,为母材强度的96%.     

In situ hot-pressed ZrB2-based composite with polycarbosilane-derived SiC: Microstructure and mechanical behavior

In this study, a homogenously dispersed finer SiC particles-containing ZrB₂ composite was prepared using nanosized polycarbosilane (PCS) particles-containing ZrB₂ mixture powder, followed by hot pressing. The microstructure of the resulting composite was characterized by field-emission scanning electron microscopy and transmission electron microscopy. The composite microstructure comprised finer equiaxed ZrB₂ and SiC grains. The mechanical behavior of the composite was evaluated using four-point bending test at different temperatures between room temperature (RT) and 1600°C. The results show that the composite exhibited only linear deformation behavior prior fracture at or below 1500°C. However, a trace quantity of nonlinear deformation was observed at 1600°C. In addition, the flexural strength of the composite decreased as the temperature increased from RT to 1200°C, then the strength increased as the temperature raised to 1400°C. Subsequently, the flexural strength remained almost the constant between 1400°C and 1600°C, with a strength of ~760 MPa.     

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.     

Si3N4/TiC纳米复合陶瓷刀具材料氧化行为

在微米Si3N4基体中加入纳米Si3N4及TiC颗粒,以Al2O3和Y2O3作为助烧结剂,通过热压烧结制备了Si3N4/TiC纳米复合陶瓷刀具材料,研究了该材料在800～1 250℃时的氧化行为.结果表明:该类材料的氧化特性符合抛物线规律;随TiC含量的增加,材料的抗氧化性能降低.由氧化后样品的X射线衍射谱分析可知:氧化表面生成SiO2和TiO2,表面仅余微量的Si3N4和TiC成分,表明经1 250℃,100h氧化后,样品表面几乎被氧化物覆盖.Si3N4/TiC(含有10%纳米Si3N4和15%TiC,质量分数)纳米复合材料在经过900℃,100h氧化后,其强度无明显下降;但经过1000℃,100h的氧化后,材料的强度已经降至氧化前的41%.扫描电镜观察表明裂纹的生成及扩展是引起强度降低的主要原因.     

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.     

多孔Si3N4-SiO2复相陶瓷及其性能

采用近净尺寸成型制备工艺-氧化烧结结合溶胶浸渍再烧结法,制备了多孔Si3N4-SiO2复相陶瓷.讨论了制各工艺对材料的成分、微结构和性能的影响规律.研究表明:随着硅溶胶浸渍量的增加,材料的抗弯强度、硬度、断裂韧性、密度和介电常数均增大.分别采用压痕法和单边切口梁法对材料的断裂韧性进行了测定和比较.结果表明:采用压痕法测定断裂韧性时,多孔Si3N4-SiO2复相陶瓷的增韧机理有裂纹偏转、裂纹分叉、裂纹桥接以及孔的钝化.采用单边切口梁法测定断裂韧性时,多孔Si3N4-SiO2复相陶瓷的增韧机理只有裂纹偏转.     

Oxidation Effects on the Mechanical Properties of a SiC-Fiber-Reinforced Reaction-Bonded Si3N4 Matrix Composite

The room-temperature mechanical properties of a SiC-fiberreinforced reaction-bonded silicon nitride composite were measured after 100 h treatment in nitrogen and oxygen environments to 1400°C. The composite heat-treated in nitrogen to 1400°C showed no appreciable loss in properties. In contrast, composites heat-treated in oxygen from 600° to 1000°C retained ∼65% and 35% of the matrix fracture and ultimate strength, respectively, of the as-fabricated composites, and those heat-treated from 1200° to 1400°C retained greater than 90% and 65% of the matrix fracture and ultimate strength, respectively, of the as-fabricated composites. For all nitrogen and oxygen treatments, the composite displayed strain capability beyond the matrix fracture strength. Oxidation of the fiber surface coating, which caused degradation of bond between the fiber and matrix and reduction in fiber strength, appears to be the dominant mechanism for property degradation of the composites oxidized from 600° to 1000°C. Formation of a protective silica coating at external surfaces of the composites at and above 1200°C reduced oxidation of the fiber coating and hence degrading effects of oxidation on their properties.     

聚苯硫醚/纳米Si3N4复合材料的制备及性能研究

表面改性处理的纳米Si3N4粉体与聚苯硫醚（PPS）熔融共混挤出制成PPS/纳米Si3N4复合材料,通过拉伸、冲击实验及动态力学性能测试考察了纳米粉体加入量对复合体系各项性能的影响。结果表明,纳米Si3N4填充PPS基复合材料的力学性能明显优于纯PPS。随粉体添加量的增加,复合材料的拉伸强度增大,当添加量为0.8 %时,拉伸强度提高了22 %。随粉体添加量的增加,复合体系冲击强度增大,当粉体添加量为1.2 %时,冲击强度和缺口冲击强度出现最大值,分别比纯PPS增加了33 %和41 %。动态力学性能测试表明,随粉体添加量的增加,PPS分子链段松弛所需能量增加,松弛过程增长,体系储能模量降低,损耗模量增加。