Sintered Reaction-Bonded Silicon Nitride with High Thermal Conductivity and High Strength

Sintered reaction-bonded silicon nitride (SRBSN) materials were prepared from a high-purity Si powder doped with Y₂O₃ and MgO as sintering additives by nitriding at 1400°C for 8 h and subsequently postsintering at 1900°C for various times ranging from 3 to 24 h. Microstructures and phase compositions of the nitrided and the sintered compacts were characterized. The SRBSN materials sintered for 3, 6, 12, and 24 h had thermal conductivities of 100, 105, 117, and 133 W/m/K, and four-point bending strengths of 843, 736, 612, and 516 MPa, respectively. Simultaneously attaining thermal conductivity and bending strength at such a high level made the SRBSN materials superior over the high-thermal conductivity silicon nitride ceramics that were prepared by sintering of Si₃N₄ powder in our previous works. This study indicates that the SRBSN route is a promising way of fabricating silicon nitride materials with both high thermal conductivity and high strength.     

Thermal Conductivity of Gas-Pressure-Sintered Silicon Nitride

Si₃N₄ with high thermal conductivity (120 W/(m^.K)) was developed by promoting grain growth and selecting a suitable additive system in terms of composition and amount. β-Si₃N₄ doped with Y₂O₃-Nd₂O₃ (YN system) or Y₂O₃-A1₂O₃ (YA system) was sintered at 1700°-2000°C. Thermal conductivity increased with increased sintering temperature because of decreased two-grain junctions, as a result of grain growth. The effect of the additive amount on thermal conductivity with the YN system was rather small because increased additive formed multigrain junctions. On the other hand, with the YA system, thermal conductivity considerably decreased with increased additive amount because the aluminum and oxygen in the YA system dissolved into β-Si₃N₄ grains to form a β-SiAlON solid solution, which acted as a point defect for phonon scattering. The key processsing parameters for high thermal conductivity of Si₃N₄ were the sintering temperature and additive composition.     

高热导率氮化铝陶瓷研究进展

氮化铝(AIN)陶瓷具有热导率高、热膨胀系数低、电阻率高等特性以及良好的力学性能,被认为是新一代高性能陶瓷基片和封装的首选材料.本文简要介绍了氮化铝陶瓷的基本特性,重点总结了氮化铝陶瓷的国内外研究现状及其制备工艺,并列举了一些氮化铝陶瓷的应用实例.     

Development of High Thermal Conductivity Aluminum Nitride Ceramic

AIN ceramics with densities varying from 3.18 to 3.30 g/cm³ and room-temperature thermal conductivities varying from 88 to 193 W/m K were produced. Different sintering conditions, packing powders, AIN powder sources, carbon additive, and sintering times were evaluated, and the key processing parameters which cause the differences in density and thermal conductivity were identified. SEM, TEM, and EDS were used to characterize the correlation between thermal conductivity, microstructure, and processing parameters. The important parameters which control the thermal conductivity of AIN ceramics are discussed.     

低热导率磷酸锆结合氮化硅多孔陶瓷的制备

采用无压烧结工艺制备ZrP2O7结合Si3N4多孔陶瓷,研究了孔隙率对材料抗弯强度和热导率的影响.结果表明:当孔隙率为20％q3％时,热导率为0.4～1.9 W/(m·K);当孔隙率为20％时,热导率下降至1.9 W/(m·K),但力学性能并没有明显降低.当Effective Medium Theory模型的比例系数为0.3、Maxwell-Eucken2模型的比例系数为0.7时,计算所得热导率与实验结果相符.     

Microstructure and Thermal Conductivity of Silicon Carbide with Yttria and Scandia

A fully dense SiC ceramic with high thermal conductivity was obtained by conventional hot pressing, with 1 vol% Y₂O₃–Sc₂O₃ additives. The ceramic had a bimodal microstructure consisting of large and small equiaxed SiC grains. Observation with high‐resolution transmission electron microscopy (HRTEM) showed two kinds of homophase (SiC/SiC) boundaries, that is crystallized and clean boundaries, and a fully crystallized junction phase. The thermal conductivity of the SiC ceramic was 234 W (m·K)^?1 at room temperature. The high thermal conductivity was attributed to a clean SiC lattice and good contiguity between SiC grains.     

缺陷对氮化硅导热性能影响的模拟研究

通过反应或热压烧结制备氮化硅器件过程中,产生的晶格空位和杂质氧等缺陷会严重影响氮化硅材料的导热性能。为了探究空位和氧杂质对氮化硅材料导热性能的影响规律,利用分子动力学模拟方法设计了多种不同缺陷状态的氮化硅模型,分析了空位/氧杂质的比例、分布状态、晶格位置以及温度对氮化硅材料导热性能的影响。研究结果表明:随着空位/氧杂质比例的增加以及温度的升高,氮化硅体系的热导率都呈明显的下降趋势;当空位/氧杂质由原本随机分布逐渐向导热通路中间聚集时,氮化硅的热导率急剧降低;空位/氧杂质所处不同晶格位置,体系热导率有明显差异。另外,通过计算氮化硅模型的声子态密度,进一步验证了空位/氧杂质比例以及温度对体系导热性能的影响规律。研究结果为制备具有高导热性的氮化硅陶瓷提供了重要的指导。     

Spark Plasma Sintered Silicon Nitride Ceramics with High Thermal Conductivity Using MgSiN2 as Additives

Silicon nitride ceramics were prepared by spark plasma sintering (SPS) at temperatures of 1450°–1600°C for 3–12 min, using α-Si₃N₄ powders as raw materials and MgSiN₂ as sintering additives. Almost full density of the sample was achieved after sintering at 1450°C for 6 min, while there was about 80 wt%α-Si₃N₄ phase left in the sintered material. α-Si₃N₄ was completely transformed to β-Si₃N₄ after sintering at 1500°C for 12 min. The thermal conductivity of sintered materials increased with increasing sintering temperature or holding time. Thermal conductivity of 100 W·(m·K)⁻¹ was achieved after sintering at 1600°C for 12 min. The results imply that SPS is an effective and fast method to fabricate β-Si₃N₄ ceramics with high thermal conductivity when appropriate additives are used.     

Microstructure Characterization in Superplastically Deformed Silicon Nitride

Fully dense silicon nitride (Si₃N₄) has been produced by hot isostatically pressing α-Si₃N₄ powder at 1740°C under 160 MPa, with 0.5 wt% Y₂O₃ and 0.5 wt% Al₂O₃ as sintering additives. The sintered material was composed of very fine (0.5 μm) and equiaxed grains, as required for superplasticity. Before deformation, a very small amount of intergranular glassy silicate-based film was detected by transmission electron microscopy at the two-grain and triple-point junctions. Compression tests with a strain value of up to }0.5 were conducted in nitrogen in the temperature range of 1600°–1700°C. The observation of a shear-thickening phenomenon and the presence of a transition from a mild to a strong strain hardening at 20 MPa were attributed to the occurrence of rigid contacts between the grains. The angular distribution of the observed strain whorls was used to evidence the increase of rigid contacts between the grains, under the local expulsion of the wetting liquid film, with increases in compressive stress.     

High Thermal Conductivity Aluminum Nitride Substrates Prepared by Aqueous Tape Casting

High thermal conductivity aluminum nitride (AlN) substrates were prepared by aqueous tape casting. The characteristics of surface-treated AlN powder were studied in aqueous ball-milling media. The oxygen content of AlN powder with the dispersant was lower than that of AlN powder without the dispersant at the same ball-milling time. The isoelectric points of the surface-treated AlN with and without a dispersant were, respectively, at pH∼3.35 and pH∼3.90. The atmosphere had considerable effects on organic additive burnout of aqueous AlN green sheets. The composition of grain boundaries changed with increasing holding time at 1850°C. A translucent AlN substrate with a uniform microstructure and a thermal conductivity of 263 W·(m·K)⁻¹ was obtained by pressureless sintering at 1850°C for 6 h in a nitrogen atmosphere.     

Role of the Interfacial Thermal Barrier in the Effective Thermal Diffusivity/Conductivity of SiC-Fiber-Reinforced Reaction-Bonded Silicon Nitride

Experimental thermal diffusivity data transverse to the fiber direction for composites composed of a reaction bonded silicon nitride matrix reinforced with uniaxially aligned carbon-coated silicon carbide fibers indicate the existence of a significant thermal barrier at the matrix-fiber interface. Calculations of the interfacial thermal conductances indicate that at 300°C and 1-atm N₂, more than 90% of the heat conduction across the interface occurs by gaseous conduction. The magnitude of the interfacial conductance is decreased significantly under vacuum or by removal of the carbon surface layer from the fibers by selective oxidation. Good agreement is obtained between thermal conductance values for the oxidized composite at 1 atm calculated from the thermal conductivity of the N₂ gas and those inferred from the data for the effective composite thermal conductivity.     

Superplastic Sinter-Forging of Silicon Nitride with Anisotropic Microstructure Formation

The microstructure and mechanical properties of silicon nitride, produced by a superplastic sinter-forging technique, were investigated. The obtained silicon nitride exhibited a highly anisotropic microstructure, where rod-shaped grains tended to be aligned perpendicular to the forging direction. A very high bending strength of 2108 MPa as well as a high fracture toughness of 8.3 MPam^1/2 were achieved when a stress was applied perpendicularly to the pressing direction. This very high strength was considered to be due to the reduced flaw size by the superplastic sinter-forging process and the steep R -curve behavior caused by the grain alignment.     

Fabrication and Microstructure of Silicon Nitride/Boron Nitride Nanocomposites

A chemical process for fabrication of Si₃N₄/BN nanocomposite was devised to improve the mechanical properties. Si₃N₄/BN nanocomposites containing 0 to 30 vol% hexagonal BN ( h -BN) were successfully fabricated by hot-pressing α-Si₃N₄ powders, on which turbostratic BN ( t -BN) with a disordered layer structure was partly coated. The t -BN coating on α-Si₃N₄ particles was prepared by reducing and heating α-Si₃N₄ particles covered with a mixture of boric acid and urea. TEM observations of this nanocomposite revealed that the nanosized hexagonal BN ( h -BN) particles were homogeneously dispersed within Si₃N₄ grains as well as at grain boundaries. As expected from the rules of composites, Young's modulus of both micro- and nanocomposites decreased with an increase in h -BN content, while the fracture strength of the nanocomposites prepared in this work was significantly improved, compared with the conventional microcomposites.     

Microstructure and Properties of Self-Reinforced Silicon Nitride

Problems associated with manufacturing Si₃N₄/SiC-whisker composites have been overcome by developing selfreinforced Si₃N₄ with elongated β-Si₃N₄ grains formed in situ from oxynitride glass. This Si₃N₄–Y₂O₃–MgO–SiO₂–CaO-based material has a flexure strength >1000 MPa and fracture toughness >8 MPa·m^½. The optimum combination of mechanical properties has been obtained with Y₂O₃:MgO ratios ranging from 3:1 to 1:2, CaO contents ranging from 0.1 to 0.5 wt%, and Si₃N₄ contents between 90 and 96 wt%.     

High-Temperature Microstructure of a Hot-Pressed Silicon Nitride

The outstanding question as to the microstructure of silicon nitride at temperatures associated with potential high-temperature applications of the material is addressed experimentally by quenching thin (transmission electron microscopy) samples from 1450°C and examining them in the microscope. The morphology of the microstructure is qualitatively unchanged compared to the materials slowly cooled, for example, after hot-pressing, to room temperature. The most significant difference is that the thickness of the intergranular phase is larger, typically 2 to 10 nm, as compared to the ∼ 1 nm observed in the hot-pressed material. In addition there is an apparent increase in the volume fraction of the intergranular phase at the three-grain junctions. On the basis of a number of supporting experiments including both hot-stage transmission electron microscopy (up to 1000°C) and Auger electron spectroscopy of material fractured and examined at 850°C, the change in microstructure is concluded to occur at temperatures above about 1000°C.     

Role of Interfacial Carbon layer in the Thermal Diffusivity/Conductivity of Silicon Carbide Fiber-Reinforced Reaction-Bonded Silicon Nitride Matrix Composites

The role of an interfacial carbon coating in the heat conduction behavior of a uniaxial silicon carbide nitride was investigated. For such a composite without an interfacial carbon coating the values for the thermal conductivity transverse to the fiber direction agreed very well with the values calculated from composite theory using experimental data parallel to the fiber direction, regardless of the ambient atmosphere. However, for a composite made with carbon-coated fibers the experimental values for the thermal conductivity transverse to the fiber direction under vacuum at room temperature were about a factor of 2 lower than those calculated from composite theory assuming perfect interfacial thermal contact. This discrepancy was attributed to the formation of an interfacial gap, resulting from the thermal expansion mismatch between the fibers and the matrix in combination with the low adhesive strength of the carbon coating. In nitrogen or helium the thermal conductivity was found to be higher because of the contribution of gaseous conduction across the interfacial gap. On switching from vacuum to nitrogen a transient effect in the thermal diffusivity was observed, attributed to the diffusion-limited entry of the gas phase into the interfacial gap. These effects decreased with increasing temperature, due to gap closure, to be virtually absent at 1000°C.     

High Thermal Conductivity Nanocomposites Based on Conductive Polyaniline Nanowire Arrays on Boron Nitride

With the development of soft electronics, conductive composites are garnering an increasing amount of attention. The electrical conductivity, thermal conductivity, and electrical stability of conductive composites are all very important. In particular, the thermal conductivity of conductive composites is critical to the stability of their conductive properties. However, little is reported on thermal management in conductive systems. Herein, sufficiently hydroxylated boron nitride nanosheets (BN‐OH)@polyaniline (PANI) composite nanosheets with a high thermal conductivity and outstanding conductance stability are reported. PANI nanowire arrays are aligned vertically on BN‐OH. This well‐ordered nanostructure provides the means to form a good conductive and thermally conductive path. Notably, the composite through‐plane thermal conductivity is 2.1 W m^?1 K^?1(≈1000% that of pure PANI) and that the resistivity of the composite is 1.38 Ω cm. Importantly, the resistivity of the composite remains unchanged after 1 h of work. The results show that this composite has prospective applications for use in soft electronics.     

Strength of Silicon Nitride after Thermal Shock

A water-quenching technique was used to evaluate the thermal-shock strength behavior of silicon nitride (Si₃N₄) ceramics in an air atmosphere. When the tensile surface was shielded from air during the heating and soaking process, the quenched specimens showed a gradual decrease in strength at temperatures above 600°C. However, the specimens with the air-exposed surface exhibited a ∼16% and ∼29% increase in strength after quenching from 800° and 1000°C, respectively. This is because of the occurrence of surface oxidation, which may cause the healing of surface cracks and the generation of surface compressive stresses. As a result, some preoxidation of Si₃N₄ components before exposure to a thermal-shock environment is recommended in practical applications.