Elastic–plastic analysis of ultrafine-grained Si2N2O–Si3N4 composites by nanoindentation and finite element simulation

Ultrafine-grained Si₂N₂O–Si₃N₄ composites are fabricated by hot-press sintering of amorphous nano-sized silicon nitride powders at 1600, 1650, and 1700 °C with nano-sized Al₂O₃ and Y₂O₃ as additives. Sintered materials of increasing average grain sizes of 280, 360, and 480 nm were obtained with increasing sintering temperature. Hardness and elastic modulus are tested by nanoindentation. Finite element simulations of the nanoindentation are performed to study the elastic and plastic mechanical properties based on the elastic modulus and P–h curve that were obtained through the nanoindentation tests. A theoretical method is proposed for calculating the stress–strain relationship of brittle ceramic materials based on the experimental nanoindentation data. Several relevant coefficients in the theoretical calculation formula are determined by comparing the calculation and simulation results.     

Influence of the heat treatment on mechanical properties and oxidation resistance of SiC–Si3N4 composites

The basic mechanical properties and oxidation behaviour of liquid-phase-sintered SiC–Si₃N₄ composites were investigated as a function of the heat treatment at oxidising condition at 1350 °C/0–204 h. The results were compared to those obtained for a reference silicon carbide material, prepared by the same fabrication route. The heat treatment at higher temperature had a positive effect on fracture toughness values but no changes of hardness were observed. It was shown that the oxidation resistance increases with increasing temperature of heat treatment from 1650 °C to 1850 °C. Oxidation always followed parabolic rate law indicating diffusion as the rate limiting mechanisms. The addition of silicon nitride content had no significant influence on oxidation resistance of SiC–Si₃N₄ composites.     

Formation mechanism of elongated β–Si3N4 crystals in Fe–Si3N4 composite via flash combustion

Elongated β–Si₃N₄ crystals have a significant influence on the mechanical property of Fe–Si₃N₄ composite. In this paper, the formation mechanism of elongated β–Si₃N₄ crystals in Fe–Si₃N₄ composite was investigated. During the preparation process, β–Si₃N₄ crystals developed in a spiral and layer growth mechanism in the dense areas. They kept growing from the dense areas and formed radially distributed elongated crystals with hexagonal prismatic morphology as time went on. As for the formation mechanism, the (100) crystal plane of β–Si₃N₄ from Si-N-O melt is mainly the vicinal crystal planes growth with different angles from the (100) crystal plane. At the later stage, the crystallization and the diffusion forces in Si-N-O molten phase decreased. However, the short range diffusion remained active and resulted in the gradient distribution of N content near the boundary. With the temperature decreasing, the disappearance of the short range diffusion implied the end of the crystallization process of the elongated β–Si₃N₄ crystals.     

Synthesis and properties of AlN/MAS/Si3N4 ternary glass-ceramic composites with in-situ grown rod-like β-Si3N4 crystals

The AlN/MAS/Si₃N₄ ternary composites with in-situ grown rod-like β-Si₃N₄ were obtained by a two-step sintering process. The microstructure analysis, compositional investigation as well as properties characterization have been systematically performed. The AlN/MAS/Si₃N₄ ternary composites can be densified at 1650 °C in nitrogen atmosphere. The in-situ grown rod-like β-Si₃N₄ grains are beneficial to the improvement of thermal, mechanical, and dielectric properties. The thermal conductivity of the composites was increased from 14.85 to 28.45 W/(m K) by incorporating 25 wt% α-Si₃N₄. The microstructural characterization shows that the in-situ growth of rod-like β-Si₃N₄ crystals leads to high thermal conductivity. The AlN/MAS/Si₃N₄ ternary composite with the highest thermal conductivity shows a low relative dielectric constant of 6.2, a low dielectric loss of 0.0017, a high bending strength of 325 MPa, a high fracture toughness of 4.1 MPa m^1/2, and a low thermal expansion coefficient (α_{25–300 °C}) of 5.11 × 10^?6/K. This ternary composite with excellent comprehensive performance is expected to be used in high-performance electronic packaging materials.     

Si3N4粉粒度对振荡压力烧结Si3N4陶瓷的影响

为了提高Si₃N₄陶瓷的烧结致密度,采用振荡压力烧结工艺分别在1 745和1 775℃制备了Si₃N₄陶瓷,主要研究了Si₃N₄粉的粒度（平均粒径分别为0.4、2.0、2.3μm）对Si₃N₄陶瓷的显微结构和性能的影响。结果显示：1)在两种温度的振荡压力烧结工艺下,由三种不同粒度的Si₃N₄粉制备的Si₃N₄陶瓷的相对密度都很大,为99.65%～99.86%,彼此相差很小。2)由平均粒径为0.2μm的Si₃N₄粉在1 745℃烧结制备的试样的微观结构最均匀,其β-Si₃N₄晶粒平均长径比、抗弯强度和维氏硬度均最大,分别达到5.0、（1 364±65） MPa和（15.72±0.8） GPa;由平均粒径为2.3μm的Si₃     

Effects of whisker-like β-Si3N4 seeds on phase transformation and mechanical properties of α/β Si3N4 composites using MgSiN2 as additives

α/β Si₃N₄ composites with β-Si₃N₄ content ranging from 26% to 100% were hot-pressed with or without β-Si₃N₄ seeds, using MgSiN₂ as additives, and their mechanical properties were investigated. When the α-Si₃N₄ content was over 58%, the microhardness of α/β Si₃N₄ composites was in the range of 23–24 GPa, and then the indentation hardness decreases with decreasing the content of α-Si₃N₄, whether with β-Si₃N₄ seeds or not. The toughness increased with increasing elongated β-Si₃N₄ grains, which improved fracture resistance by crack bridging, pull out or the crack deflection mechanism, and reached the maximum value of 7.0 MPa m^1/2 with 1 wt% β-seeds. In comparison with α/β Si₃N₄ composite with a similar phase composition, the fracture strength was improved by adding β-Si₃N₄ seeds because of the relatively smaller grain sizes and higher toughness. The α/β Si₃N₄ composite with 5 wt% β-seeds showed a high strength of 1253 MPa, a high hardness of 20.9 GPa and a toughness of 6.9 MPa m^1/2.     

Sn/Si3N4复合镀层中纳米Si3N4含量测定方法的比较

采用电熔解法溶解Sn/Si3N4复合镀层,以紫外可见分光光度法测定了镀层中纳米Si3N4的含量,并与传统酸溶解及重量法对比。结果表明,电解法在10 min内使镀层完全溶解且在测定波长448 nm处纳米Si3N4溶液的吸光度值与其浓度在10～200 mg/L范围保持良好的线性关系,该方法简单,省时,误差小,回收率98.5%～100%。     

Microstructure and reaction phases in Si3N4/Si3N4 joint brazed with Cu–Pd–Ti filler alloy

Si₃N₄ ceramic was self-jointed using a filler alloy of Cu–Pd–Ti, and the microstructure of the joint was analyzed. By using a filler alloy of Cu76.5Pd8.5Ti15 (at.%), a high quality Si₃N₄/Si₃N₄ joint was obtained by brazing at 1100–1200 °C for 30 min under a pressure of 2 × 10⁻³ MPa. The microstructure of the Si₃N₄/Si₃N₄ joint which was observed by EPMA, XRD and TEM, and the results indicated that a reaction layer of TiN existed at the interface between Si₃N₄ ceramic and filler alloy. The center of the joint was Cu base solid solution containing Pd, and some reaction phases of TiN, PdTiSi and Pd₂Si found in the Cu [Pd] solid solution.     

Microstructure evolution of Si3N4/Si3N4 joint brazed with Ag–Cu–Ti + SiCp composite filler

The Si₃N₄ ceramic was brazed by Ag–Cu–Ti + SiCp composite filler (p = particle) prepared by mechanical mixing. Effects of the content of Ti and SiC particles on microstructure of the joint were investigated. A reliable Si₃N₄/Si₃N₄ joint was achieved by using Ag–Cu–Ti + SiCp composite filler at 1173 K for 10 min. A continuous and compact reaction layer, with a suitable thickness, forms at the Si₃N₄/braze interface. The SiC particles react with Ti in the brazing layers, forming Ti₃SiC₂ thin layers around the SiC particles themselves and Ti₅Si₃ small particles in the Ag[Cu] and Cu[Ag] based solid solution. The higher content of SiC particles in the filler (≥10 vol%) depresses interfacial bonding strength between the Si₃N₄ substrate and composite brazing layer due to the thinner reaction layer and the bad fluidity of the filler. The Ti₃SiC₂ → TiC + Ti₅Si₃ reaction occurs when Ti concentration around SiC particles in the filler increases.     

In situ preparation of Si3N4–TiN composite by pyrolysis of polytitanosilazane (PTSZ)

Si₃N₄–TiN composite powders were obtained by in situ pyrolysis of polytitanosilazane. Dense Si₃N₄–TiN composites were prepared by hot-pressing at 1800 °C under 20 MPa for 2 h without sintering additive. Crystallization of amorphous PTSZ powders occurred between 1400 and 1500 °C with major phases, α-Si₃N₄, β-Si₃N₄, and small amount of phase TiN. Mechanical properties and microstructure of Si₃N₄–TiN composites were characterized. The results showed that the mechanical strength was 620 MPa, the fracture toughness was 7.8 MPa m^1/2 and the Vickers hardness was 8.5 GPa. SEM analysis indicated that Si₃N₄–TiN composite possessed excellent fracture toughness because TiN grains produced by in situ pyrolysis were well dispersed in Si₃N₄ matrix.     

Dielectric relaxation properties of PbTiO3-multiwalled carbon nanotube composites prepared by a sol–gel process

Dielectric composites fabricated by combining multi-walled carbon nanotubes (MWCNT) and PbTiO₃ (PTO) powder were prepared using a sol–gel process. Well-dispersed PTO powder with various volume ratios of MWCNT was compressed to form a pellet, and then silver electrodes were coated on both sides for electrical measurements. The PTO–MWCNT composite with 0.4 vol% MWCNT showed the highest dielectric constant (912 at 1 kHz), which is approximately 25 times larger than that (37 at 1 kHz) of a pure PbTiO₃ pellet. Furthermore, a strong frequency dependence of the dielectric constant in the low frequency range was shown for the PTO–MWCNT composites. Interfacial effects related to dielectric relaxation in composite materials were used to explain an observed increase of the dielectric constant near the percolation threshold.     

Fabrication and wear behaviors of graded Si3N4 ceramics by the combination of two-step sintering and β-Si3N4 seeds

Graded Si₃N₄ ceramics with sandwich-like microstructure were fabricated by the combination of hot-pressing, spark plasma sintering and β-Si₃N₄ seeds. Phase compositions, microstructures, mechanical properties, and wear behaviors were investigated. Main α-Si₃N₄ phase were detected in the outer layers, and only β-Si₃N₄ phase were observed in the inner layers. The outer layer with ultra-fine equiaxed grains were well bonded to the inner layer with a distinct bimodal grain size distribution. Vickers hardness of outer layer (～21.2?GPa) was much higher than that of inner layer (～16.1?GPa), whereas fracture toughness of outer layer (～3.5?MPa?m^1/2) was much lower than that of inner layer (～5.9?MPa?m^1/2), indicative of the hard surface and tough core. Due to the ultra-fine microstructure and high hardness of outer layer, the graded Si₃N₄ ceramics exhibited superior wear resistance with low wear rate.     

Joining of Si3N4 to Si3N4 using a AuPd(Co,Ni)–V filler alloy and the interfacial reactions

Au38.0–Pd28.0–Co18.0–Ni7.0–V9.0 (in wt%) alloy was designed as a filler for joining Si₃N₄. The filler alloy showed a contact angle of 77.2° on Si₃N₄ ceramic at 1473 K. The Si₃N₄/Si₃N₄ joint brazed with the rapidly-solidified filler foils at 1443 K for 10 min exhibits an average three-point bend strength of 320.7 MPa at room temperature and the strength values are 217.9 MPa and 102.9 MPa at 1073 K and 1173 K respectively. The interfacial reaction products were composed of V₂N and Pd₂Si, and the elements Co and Ni in the brazing alloy did not participate in the interfacial reactions. The coarse-network-like distribution of refractory Pd₂Si compound within the Au–Pd–Co–Ni alloy matrix throughout the joint contributes to the stable high-temperature joint strengths.     

Simultaneous synthesis and consolidation of nanostructured TaSi2–Si3N4 composite by pulsed current activated combustion

Dense nanostructured 4TaSi₂–Si₃N₄ composite was synthesized by pulsed current activated combustion synthesis (PCACS) method within 3 min in one step from mechanically activated powders of TaN and Si. Simultaneous combustion synthesis and densification were accomplished under the combined effects of a pulsed current and mechanical pressure. Highly dense 4TaSi₂–Si₃N₄ composite with relative density of up to 98% was produced under simultaneous application of a 60 MPa pressure and the pulsed current. The average grain size and mechanical properties (hardness and fracture toughness) of the composite were investigated.     

低温热压制备高硬度、高韧性Si3N4–SiCw–ZrB2陶瓷

通常低温热压烧结的Si₃N₄陶瓷具有较高的硬度和较低的断裂韧性;而高温热压烧结的Si₃N₄陶瓷具有较低的硬度和较高的断裂韧性。为了获得高硬度、高韧性Si₃N₄陶瓷,添加20%SiC_w（SiC晶须,体积分数）和2.5%ZrB2,在1 500℃低温热压制备了Si₃N₄基陶瓷,开展其相组成、致密度、显微结构和力学性能研究,并与1 800℃高温热压烧结Si₃N₄进行了对比研究。结果表明：SiC_w的引入阻碍了Si₃N₄低温致密化,致密度从97.9%降低到92.9%,Vickers硬度从20.5 GPa降低到16.4 GPa,断裂韧性从2.9 MPa·m^1/2增加到3.4 MPa·m^1/2。同步引入SiC_w和ZrB₂     

Paper derived SiC–Si3N4 ceramics for high temperature applications

Biomorphic Si₃N₄–SiC ceramics have been produced by chemical vapour infiltration and reaction technique (CVI-R) using paper preforms as template. The paper consisting mainly of cellulose fibres was first carbonized by pyrolysis in inert atmosphere to obtain carbon bio-template, which was infiltrated with methyltrichlorosilane (MTS) in excess of hydrogen depositing a silicon rich silicon carbide (Si/SiC) layer onto the carbon fibres. Finally, after thermal treatment of this Si/SiC precursor ceramic in nitrogen-containing atmosphere (N₂ or N₂/H₂), in the temperature range of 1300–1450 °C SiC–Si₃N₄ ceramics were obtained by reaction bonding silicon nitride (RBSN) process. They were mainly composed of SiC containing α-Si₃N₄ and/or β-Si₃N₄ phases depending on the nitridation conditions. The SiC–Si₃N₄ ceramics have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and Raman spectroscopy. Thermal gravimetric analysis (TGA) was applied for the determination of the residual carbon as well as for the evaluation of the oxidation behaviour of the ceramics under cyclic conditions. The bending strength of the biomorphic ceramics was related to their different microstructures depending on the nitridation conditions.     

Si3N4粉体表面化学分析及表面改性

Si3N4陶瓷是一种重要的结构陶瓷,本文着重阐述了Si3N4粉体的表面分析方法,以及为了提高固相体积分数而进行的Si3N4粉体表面改性方面的进展.     

Fabrication and properties of Si3N4 bioscaffolds with orderly–interconnected big pore channels and well–distributed small pores

This paper focuses on investigating the technical potential for fabricating porous ceramic bioscaffolds for the repair of osseous defects from trauma or disease by inverse replication of three–dimensional (3–D) printed polymer template. Si₃N₄ ceramics with pore structure comprising orderly–interconnected big pore channels and well–distributed small pores are successfully fabricated by a technique combining 3–D printing, vacuum suction filtration and oxidation sintering. The Si₃N₄ ceramics fabricated from the Si₃N₄ powder with addition of 10?wt% talcum by sintering at 1250?°C for 2?h have little deformation, uniform microstructure, low linear shrinkage of 4.1%, high open porosity of 58.2%, relatively high compression strength of 6.4?MPa, orderly–interconnected big pore channels and well–distributed small pores, which are promising bioscaffold in the field of bone tissue engineering.     

导电 Si3N4 基复相陶瓷研究进展

Si_3N_4陶瓷具有优异的力学性能和导热性能,然而其固有的高硬度和脆性极大地限制了其加工性能。通过添加导电相改善Si3N4陶瓷的导电性能可实现对Si_3N_4陶瓷的电火花加工。添加的导电相主要包括钛基化合物(TiN、TiC、TiC N、TiB_2)、锆基化合物(Zr B_2、Zr N)和MoSi_2等导电陶瓷以及碳纳米管(CNT)、碳纳米纤维(CNF)、石墨烯纳米片(GNP)等导电碳基纳米材料。本论文详细回顾了Si_3N_4基导电陶瓷的研究进展,并对今后Si_3N_4基导电陶瓷的发展趋势进行了展望。