Improved sinterability of SiC(w)/Si3N4 composites by whisker-oriented alignment

Effects of whisker-oriented alignment on sintering behavior of SiC(w)/Si₃N₄ composites were investigated by sintering curves of SiC(w)/Si₃N₄ compacts with different whisker alignment (random and unidirectionally oriented). It was found that whisker-oriented alignment led to considerable anisotropy of linear shrinkage and sintering rate of SiC(w)/Si₃N₄ compacts during sintering. Whisker-oriented alignment could improve the sinterability of the SiC(w)/Si₃N₄ composites and consequently improve the maximum fraction of whisker addition and reduce the content of sintering additives without obviously lowering the density, which are more beneficial to exert the best reinforcing effects of whiskers and mechanical properties of SiC(w)/Si₃N₄ composites at elevated temperature.     

Synthesis of Si3N4 whiskers in porous SiC bodies

Si₃N₄ whiskers were synthesized by the carbothermal reduction process in porous SiC bodies. The SiC bodies had a sponge microstructure with pore sizes of approximately 600 μm. The raw materials for the Si₃N₄ whiskers were powder mixtures of Si₃N₄, SiO₂ and Si for silicon and phenolic resin for carbon. Cobalt was used as a metal catalyst. The carbothermal reaction was performed at 1400 °C or 1500 °C for 1 or 2 h. The α-Si₃N₄ whiskers grew inside the SiC pores by the VLS process, and their diameters ranged from 0.1 to 1.0 μm. The length of the grown Si₃N₄ whiskers was over 100 μm and their growth direction was [100].     

颗粒级配对Si_(3)N_(4)w/Si_(3)N_(4)复合材料弯曲强度与介电性能的影响EI北大核心CSCD

为了获得一种弯曲和介电性能良好的氮化物陶瓷材料,本工作首先以氮化硅晶须(Si_(3)N_(4w))为原料,采用喷雾造粒工艺制备3种具有不同粒径分布的Si_(3)N_(4w)球形颗粒粉体,研究雾化盘转速对Si_(3)N_(4w)球形颗粒粉体粒径分布的影响。然后以喷雾造粒得到的Si_(3)N_(4w)球形颗粒为原料,采用干压法制备3种颗粒级配的Si_(3)N_(4w)预制体,研究颗粒级配Si_(3)N_(4w)预制体的孔径分布。采用化学气相渗透(CVI)和先驱体浸渍裂解(PIP)工艺在3种颗粒级配的Si_(3)N_(4w)预制体中进一步制备Si_(3)N_(4)基体,研究Si_(3)N_(4w)/Si_(3)N_(4)复合材料制备过程中的物相和微结构演变以及颗粒级配对Si_(3)N_(4w)/Si_(3)N_(4)复合材料的微结构、密度、弯曲强度和介电性能的影响。结果表明:3种颗粒级配的Si_(3)N_(4w)预制体均具有二级孔隙特征,其中小孔孔径均约为0.7μm,大孔孔径分别为45.2,30.1μm和21.3μm。在制备的3种颗粒级配的Si_(3)N_(4w)/Si_(3)N_(4)复合材料中,S13样品的颗粒级配效果最好,复合材料的弯曲强度达到81.59 MPa。此外,该样品的介电常数和介电损耗分别为5.08和0.018。良好的弯曲强度和介电性能表明制备的Si_(3)N_(4w)/Si_(3)N_(4)复合材料有望应用于导弹天线罩领域。     

Investigation of the physical and mechanical properties of hot-pressed machinable Si3N4/h-BN composites and FGM

A new design method of machinable ceramic composites was proposed, which applies the graded-structure concept to the design of machinable Si₃N₄ ceramics. Silicon nitride/hexagonal boron nitride (h-BN) ceramic composites and functionally graded materials were fabricated by hot pressing at 1750 °C for 2 h, varying the alignment of the amount of hexagonal BN using powder layering method. The improved machinability of Si₃N₄/h-BN composite can be attributed to addition of layered structure hexagonal BN. Hexagonal BN possesses excellent cleavage planes perpendicular to the c-axis. Ease of machining depends on degree of crystal interlocking; hence volume content of h-BN crystals and their aspect ratio affect machinability. The texture of h-BN and β-Si₃N₄ was observed during hot pressing sintering. Physical and mechanical properties of Si₃N₄/h-BN with different content of h-BN were investigated, such as bulk density, Vickers's hardness, flexural strength, and elastic modulus. All of these properties are important for the design of the machinable Si₃N₄/h-BN FGM (Functionally Graded Materials).     

Compressive creep behavior of hot-pressed Si3N4-CRE2O3-Al2O3 ceramics

In this work, yttrium-rare earth oxide solid solution, CRE₂O₃, produced at FAENQUIL-DEMAR at a cost of only 20% of pure commercial Y₂O₃, was used as sintering additive of hot-pressed Si₃N₄ ceramics. The objective of this work was to characterize and to investigate the creep behavior of these ceramics. The samples were sintered by hot-pressing at 1750 °C, for 30 min using a pressure of 20 MPa. Compressive creep tests were carried out in air, between 1250 and 1300 °C, for 60 h, under stresses of 200-300 MPa. The stress exponent under all conditions was determined to be about unity. The apparent activation energy obtained was around 460 kJ mol⁻¹, corresponding to the heat of solution of the Si₃N₄ in the glassy phase. Both the stress exponent n and apparent activation energy Q are within the range of values reported in other studies of the compressive creep of Y₂O₃-Al₂O₃-doped-Si₃N₄ ceramics. X-ray diffraction (XRD) characterization shows a global reorientation of the β-Si₃N₄ grains and SEM observations detected no grain growth after the creep tests. These results indicate that grain-boundary sliding controlled by viscous flow is the dominant creep mechanism observed in the present study. The creep resistance presented of this samples indicates that this additive CRE₂O₃ can be a cheap alternative in the fabrication of Si₃N₄ ceramics, resulting in promising mechanical properties.     

Effect of the microstructure of Si3N4 on the adhesion strength of TiN film on Si3N4

The effect of the microstructure of silicon nitride, which was used as a substrate, on the adhesion strength of physical vapor deposited TiN film on Si₃N₄ was investigated. Silicon nitride substrates with different microstructures were synthesized by controlling the size (fine or coarse), the phase ( or β) of starting Si₃N₄ powder, and sintering temperature. The microstructure of Si₃N₄ was characterized in terms of grain size, aspect ratio of the elongated grain, and β-to- phase ratio. For a given chemical composition but different mechanical properties, such as toughness, elastic modulus, and hardness of Si₃N₄ were obtained from the diverse microstructures. Hertzian indentation was used to estimate the yield properties of Si₃N_4, such as critical loads for yield (P_y) and for ring cracking (P_c). The effect of the microstructure of Si₃N₄ on adhesion strength evaluated by scratch test is discussed. TiN films on Si₃N₄ showed high adhesion strengths in the range of 80–140 N. Hardness and the P_y of Si₃N₄ substrate were the primary parameters influencing the adhesion strength of TiN film. In TiN coating on Si₃N₄, substrates with finer grain sizes and higher phase ratios, which show high hardness and high P_y, were suitable for higher adhesion strength of TiN film.     

用聚碳硅烷为先驱体制备SiC/Si3N4纳米复相陶瓷

采用聚碳硅烷(PCS) 为先驱体, 利用原位生长法制备SiC/Si₃N₄ 纳米复相陶瓷, 其室温弯曲强度和断裂韧性达到了637M Pa 和8. 10M Pa·m1/2 。研究了材料微观结构的形成及断裂机理,指出在微观结构的形成过程中, 控制SiC 纳米微晶的生成和B-Si₃N₄ 柱状晶的生长是关键, 而增韧补强的主要原因在于形成了晶内型结构和长径比大(大于7. 5) 的Si₃N₄ 柱状晶, 从而改变了断裂机理。      

Effect of Si3N4-particles addition in Ag-Cu-Ti filler alloy on Si3N4/TiAl brazed joint

A novel composite filler alloy was developed by introducing Si₃N_4p (p = particles) into Ag-Cu-Ti filler alloy. The brazing of Si₃N₄ ceramics and TiAl intermetallics was carried out using this composite filler alloy. The typical interfacial microstructure of brazed joints was: TiAl/AlCu₂Ti reaction layer/Ag_(s,s) + Al₄Cu₉ + Ti₅Si_3p + TiN_p/TiN + Ti₅Si₃ reaction layer/Si₃N₄. Effects of Si₃N_4p content in composite filler alloy on the interfacial microstructure and joining properties were investigated. The distribution of Ti₅Si_3p and TiN_p compounds in Ag-based solid solution led to the decrease of the mismatch of the coefficient of thermal expansion (CTE) and the Young's modulus between Si₃N₄ and TiAl substrate. The maximum shear strength of 115 MPa was obtained when 3 wt.% Si₃N_4p was added in the composite filler alloy. The fracture analysis showed that the addition of Si₃N_4p could improve the mechanical properties of the joint.     

SPS制备氮化硅/锌铝基复合材料的组织和性能研究

通过放电等离子烧结工艺制备了氮化硅/锌铝基复合材料,重点探讨了氮化硅添加量对氮化硅/锌铝基复合材料致密度、硬度和摩擦性能的影响.采用扫描电子显微镜(SEM)及电子探针X射线显微分析仪(EPMA)对样品的微观组织进行了分析,并使用显微硬度仪、旋转摩擦试验仪对其性能进行了研究.结果表明:氮化硅在样品中分散均匀,且氮化硅的加...     

Study on particle-stabilized Si3N4 ceramic foams

The stability of bubbles and the microstructures of sintered Si₃N₄ ceramic foams produced by direct foaming method were investigated. The bubbles produced by short-chain amphiphiles (propyl gallate) have higher stability as compared with that produced by long-chain surfactants (TritonX-114). Si₃N₄ ceramic foams using short-chain amphiphile are particle-stabilized one, the pore cells are spherical and closed, and cell surfaces are smooth and dense. The pore cells of sintered Si₃N₄ ceramic foams using TritonX-114 foaming are coarse and large, and pore cells are polyhedral. High gas-pressure sintering is conducive to the development of the whisker-like microstructures in Si₃N₄ ceramic foams. The sintered Si₃N₄ ceramic foams with the whisker-like microstructure are quite promising for improving the mechanical strength of the ceramics by a simple and safe way.     

The effect of Si3N4 on the thermal expansion behavior of MoSi2

The effect of Si₃N₄ particulates on the thermal expansion coefficient (CTE) of MoSi₂ was investigated. It was observed that as the volume percent of Si₃N₄ increases, the CTE of the MoSi₂-Si₃N₄ composites decreases. In the temperature range 1000–1500 °C, typical of that required for glass melting, about 30–35 vol% Si₃N₄ particulates are needed in the MoSi₂-Si₃N₄ composites such that the CTE of the composite matches the CTE of Mo.     

Interfacial microstructure of Si3N4/Si3N4 brazing joint with Cu–Zn–Ti filler alloy

In this study, Si₃N₄ ceramic was jointed by a brazing technique with a Cu–Zn–Ti filler alloy. The interfacial microstructure between Si₃N₄ ceramic and filler alloy in the Si₃N₄/Si₃N₄ joint was observed and analyzed by using electron-probe microanalysis, X-ray diffraction and transmission electron microscopy. The results indicate that there are two reaction layers at the ceramic/filler interface in the joint, which was obtained by brazing at a temperature and holding time of 1223 K and 15 min, respectively. The layer nearby the Si₃N₄ ceramic is a TiN layer with an average grain size of 100 nm, and the layer nearby the filler alloy is a Ti₅Si₃N_x layer with an average grain size of 1–2 μm. Thickness of the TiN and Ti₅Si₃N_x layers is about 1 μm and 10 μm, respectively. The formation mechanism of the reaction layers was discussed. A model showing the microstructure from Si₃N₄ ceramic to filler alloy in the Si₃N₄/Si₃N₄ joint was provided as: Si₃N₄ ceramic/TiN reaction layer/Ti₅Si₃N_x reaction layer/Cu–Zn solution.     

Preparation and properties of pressureless-sintered porous Si3N4

Wave-transparent materials used at high temperature environment generated by high supersonic and hypersonic speeds must possess excellent mechanical property. In this paper, porous Si₃N₄ ceramics with high strength were fabricated by low molding pressure (10 MPa) and pressureless sintering process, without any other pore forming agents. The sintering behavior and the effect of porosity on the mechanical strength and dielectric properties were investigated. The flexural strength of porous Si₃N₄ ceramics was up to 57–176 MPa with porosity of 45–60%, dielectric constant of 2.35–3.39, and dielectric loss of 1.6–3.5 × 10⁻³ in the frequency range of 8–18 GHz, at room temperature. With the increase of porosity, the flexural strength, dielectric constant, and dielectric loss all decreased.     

Preparation of the rod-like β-Si3N4 particles favoring the self-reinforcing Si3N4 ceramics

The β-Si₃N₄ particles were prepared by heating original α-Si₃N₄ powder with rare earth oxide Nd₂O₃ or Yb₂O₃ additives at 1600-1700 °C for 1.5 h. The transformation ratio of α-Si₃N₄ was also investigated by XRD. The results showed that Yb₂O₃ could accelerate the transformation of Si₃N₄ more effectively than Nd₂O₃ and the powder heated at 1700 °C with over 4 wt.% Yb₂O₃ has a high transformation ratio of over 98%. The morphologies of the heated powders were observed by scanning electron microscopy. The results showed that the powder heated at 1700 °C with 4 wt.% Yb₂O₃ had ideal β-Si₃N₄ rod-like morphology particles. This heated powder was used as a seed by adding it to the original α-Si₃N₄ powder to prepare self-reinforced Si₃N₄ ceramic by hot-pressed sintering. The fracture toughness of the seeded Si₃N₄ ceramics increased to 9.1 MPa m^1/2 from 7.6 MPa m^1/2 of the unseeded Si₃N₄ ceramics, while the high value of strength was still kept at 1200 °C.     

Dense and near-net-shape fabrication of Si3N4 ceramics

With silicon nitride significant progress has been made in order to search for fully dense, strong, reliable structural ceramics to find wide use in applications at high temperatures which are allowing new and innovative solutions to component design problems. Taking into account that more and more ceramic components based on Si₃N₄ are being used in the aerospace and automobile industries, it is a great challenge to fabricate such complex-shaped components with high reliability and with defect-free microstructures such as pores, inclusions or any other inhomogeneity at acceptable costs. On the other side, the high hardness of Si₃N₄ ceramics is almost always cost prohibitive to shape components by hard machining. It is therefore great effort exhibited in the development of near-net-shape fabrication processes that can produce complex-shaped components with a minimum of machining as well as to minimize the number and size of microstructural defects within design limits. In this review, the fabrication of near-net-shape Si₃N₄ ceramics is given in detail. All kinds of these techniques (injection molding, gelcasting, robocasting, mold shape deposition, rapid prototyping) and their advantages and disadvantages are explained.     

Synthesis and photoluminescence of belt-shaped Si3N4 whiskers

Belt-shaped Si₃N₄ whiskers have been synthesized by a carbothermal reduction and nitridation method. The whiskers had an average width of 800 nm, width-to-thickness ratios of 4-6, and a length in the range of several tens of microns to hundreds of microns. Photoluminescence (PL) spectrum of the whiskers showed a strong blue emission peak at 410 nm, and PL lifetime measurement exhibited a rapid decay within a few nanoseconds. The growth of the whiskers was supposed to be dominated by a vapor-solid (VS) mechanism.     

凝胶注模成型制备纳米复合多孔氮化硅陶瓷

采用凝胶注模成型两步法烧结工艺,利用纳米碳粉增强,成功地制备出了具有高强度、结构比较均匀并有较高气孔率的氮化硅多孔陶瓷。借助X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线能谱(EDS)、Archimedes法和三点弯曲法等方法对多孔氮化硅陶瓷的微观结构和基本力学性能进行了研究。结果表明:在适当工艺条件下可制成平均强度>100 MPa、气孔率>60%的多孔氮化硅陶瓷。SEM照片显示气孔是由长柱状β-Si₃N₄晶搭接而成的,气孔分布均匀。XRD图谱显示有SiC生成。发育良好的柱晶结构、均匀的气孔分布以及反应生成的SiC微晶是获得高性能的主要原因。      

Large-scale synthesis of ear-like Si3N4 dendrites from SiO2/Fe composites and Si powders

Large-scale ear-like Si₃N₄ dendrites were prepared by the reaction of SiO₂/Fe composites and Si powders in N₂ atmosphere. The product was characterized by field emission scanning electron microscopy, X-ray diffraction, and transmission electron microscopy. The results reveal that the product mainly consists of ear-like Si₃N₄ dendrites with crystal structures, which have a length of several microns and a diameter of 100-200 nm. Nanosized ladder-like Si₃N₄ was also obtained when changing the Fe content in the SiO₂/Fe composites. The Si₃N₄ nanoladders have a length of hundreds nanometers to several microns and a width of 100-300 nm. The ear-like Si₃N₄ dendrites are formed from a two-step growth process, the formation of inner stem structures followed by the epitaxial growth of secondary branches.     

Some properties of annealed Si3N4 layers on GaAs

We have used Rutherford backscattering and electrical measurements to asses the efficiency of pyrolytically deposited Si₃N₄ as an encapsulant for ion-implanted GaAs.Outdiffusion of gallium and arsenic into the Si₃N₄ layers occurred in all cases, the quantity being dependent on the source of GaAs. However, we conclude that Si₃N₄ layers afford better protection than did the SiO₂ coatings that we previously investigated.     

旋转超声磨削Si3 N4陶瓷用金刚石磨具磨损行为研究

热压烧结Si₃N₄陶瓷材料常应用于航天飞行器中关键耐高温零部件,但由于高硬度和低断裂韧性,其加工效率和加工表面质量难以满足制造需求。为了提高热压烧结Si₃N₄陶瓷旋转超声磨削加工质量,减小由于金刚石磨具磨损带来的加工误差,开展了磨具磨损行为研究。基于热压烧结Si₃N₄陶瓷旋转超声磨削加工实验,分析了金刚石磨具磨损形式;基于回归分析建立了金刚石磨具磨损量数学模型,揭示了加工参数及磨具参数与金刚石磨具磨损量间映射关系;并研究了磨损形式与磨具磨损量及加工表面粗糙度影响规律。结果表明：磨粒磨耗是旋转超声磨削Si₃N₄陶瓷用金刚石磨具最主要磨损形式,比例超过50%;主轴转速和磨粒粒度对磨具磨损量影响最为显著;且磨损量较小时,加工表面粗糙度值反而增加。以上研究可为提高旋转超声磨削Si₃N₄陶瓷加工精度和加工质量提供指导。