The effect of graphene nanoplatelet thickness on the fracture toughness of Si3N4 composites

Si₃N₄ composites with 3 and 5?wt% of graphene nanoplatelet (GNP) additions were prepared by spark plasma sintering. We used both commercially available GNPs and thinner few-layer graphene nanoplatelets (FL-GNPs) prepared by further exfoliation through ball milling with melamine addition. We found that by employing thinner FL-GNPs as filler material a 100% increase in the fracture toughness of Si₃N₄/3?wt% FL-GNP composites (10.5?±?0.2?MPa?m^1/2) can be achieved as compared to the monolithic Si₃N₄ samples (5.1?±?0.3?MPa?m^1/2), and 60% increase compared to conventional Si₃N₄/3?wt% GNP composites (6.6?±?0.4?MPa?m^1/2). For 5?wt% filler content the increase of the fracture toughness was near 50% for both GNP and FL-GNP fillers. The hardness of the composites decreased with increasing GNP content. However, composites reinforced with 5?wt% of FL-GNPs displayed 30% higher Vickers hardness (12.8?±?0.2?GPa) than their counterparts comprising conventional GNP fillers (9.8?±?0.2?GPa). We attribute the enhanced mechanical properties obtained with thinner FL-GNPs to their higher aspect ratio leading to a more homogeneous dispersion, higher interface area, as well as smaller pores in the ceramic matrix.     

Enhancing toughness and strength of SiC ceramics with reduced graphene oxide by HP sintering

In this paper, the silicon carbide-reduced graphene oxide (SiC/rGO) composites with different content of rGO are investigated. The hot pressing (HP) at 2100?°C for 60?min under a uniaxial pressure of 40?M?Pa resulted in a near fully-dense SiC/rGO composite. In addition, the influence of graphene reinforcement on the sintering process, microstructure, and mechanical properties (fracture toughness, bending strength, and Vickers hardness) of SiC/rGO composites is discussed. The fracture toughness of SiC/rGO composites (7.9MPam^1/2) was strongly enhanced by incorporating rGO into the SiC matrix, which was 97% higher than the solid-state sintering SiC ceramics (SSiC) by HP. Meanwhile, the bending strength of the composites reached 625?M?Pa, which was 17.3% higher than the reference materials (SSiC). The microstructure of the composites revealed that SiC grains were isolated by rGO platelets, which lead to the toughening of the composite through rGO pull out/debonding and crack bridging mechanisms.     

Degradation evaluation of Si3N4 ceramic surface layer in contact with molten Al using microcantilever beam specimens

Although Si₃N₄ ceramics are often utilized as structural components in the Al casting industry due to their excellent properties, they occasionally suffer breakage after long-term use. In this study, the bending strength, fracture toughness, and Young’s modulus in the vicinity of the Si₃N₄ ceramic surfaces after contact with molten Al were evaluated using microcantilever beam specimens, which were fabricated using a focused ion beam technique. Fracture testing of the specimens was carried out by nanoindentation. The bending strength of the ceramic surface before and after contact with molten Al was 5.89 ± 1.33 and 3.03 ± 0.28 GPa, respectively. The fracture toughness of the corroded layer in Si₃N₄ ceramics also decreased compared to that of the polished surface. Using fractography by observation with scanning electron microscopy, it was shown that changes in the grain boundary glassy phase resulted in the degradation of strength and fracture toughness.     

Fabrication of Si3N4 ceramics with high thermal conductivity and flexural strength via novel two-step gas-pressure sintering

Si₃N₄ ceramic substrates serving as heat dissipater and supporting component are required to have excellent thermal and mechanical properties. To prepare Si₃N₄ with desirable properties, a novel two-step gas-pressure sintering route including a pre-sintering step followed by a high-temperature sintering step was devised. The effects of pre-sintering temperature (1500 – 1600 °C) on the phase transformation, microstructure, thermal and mechanical properties of the samples were studied. The pre-sintering temperature played an important role in adjusting the Si₃N₄ particles’ rearrangement and α→β transformation rate. Furthermore, the densification process for the Si₃N₄ ceramics prepared via the two-step gas-pressure sintering was revealed. After sintered at 1525 °C for 3 h followed by a high-temperature sintering at 1850 °C for another 3 h, the prepared Si₃N₄ compact with a bimodal microstructure presented the highest thermal conductivity and flexural strength of 79.42 W·m^?1·K^?1 and 801 MPa, respectively, which holds great application prospects as ceramic substrates.     

Formation mechanism of Si3N4 in reaction-bonded Si3N4-SiC composites

The formation mechanism and thermodynamics of Si₃N₄ in reaction-bonded Si₃N₄-SiC materials were analyzed. There are two kinds of Si₃N₄, fibroid α-Si₃N₄ and columnar β-Si₃N₄, which are formed by different processes in Si₃N₄-SiC materials. Silicon reacts with oxygen, forming gaseous SiO and reducing oxygen partial pressure. SiO(g) diffuses from central to peripheral sections of blocks and reacts with nitrogen, thus forming Si₃N₄, mainly in peripheral sections. The reaction between silicon and oxygen causes the consumption of oxygen and leads to low oxygen partial pressure in the sintering system, which allows silicon to react with nitrogen directly generating Si₃N₄in situ. SiO(g) reacts with nitrogen forming Si₃N₄ at both central and peripheral sections of block. The non-uniform distribution of Si₃N₄ and uneven microstructure is caused by the generation process, indicating that it is unavoidable in Si₃N₄-SiC composites.     

空气气氛中烧成Si3N4-SiC复合材料的性能、相组成和显微结构

以氮化硅细粉(粒度＜0.088 mm,w(β-Si3N4)＞95%)、碳化硅(w(SiC)＞98%,粒度分别为2.8～0.9mm、0.9～0.15 mm、＜0.115 mm和＜0.063 mm四级)、硅粉(粒度＜0.045 mm,w(Si)＞98%)和硅灰(w(SiO2)=98.3%)为原料,以木质素磺酸钙水溶液作成型结合剂,采用150 MPa的压力成型为65 mm×114 mm×230mm的Si3N4-SiC、Si3N4-SiC-Si和Si3N4-SiC-SiO2三种试样.在空气气氛中,以50℃·h-1的升温速度升至800℃保温4 h,再升至1450℃保温2 h,自然冷却至室温后,测定烧成后试样的常温耐压强度、常温抗折强度、1400℃下的高温抗折强度、显气孔率、体积密度和残氮率,并采用XRD、SEM和EPMA等手段分析烧后试样的相组成和显微结构.结果表明3种试样在空气气氛中烧成后的高温(1400℃)和常温抗折强度都比较高,显气孔率都比较低,而耐压强度则以Si3N4-SiC试样的最高;烧成后试样中心区域的残氮率以Si3N4-SiC-Si试样的最高,Si3N4-SiC-SiO2试样的次之,Si3N4-SiC试样的最小;在空气气氛中烧成后,Si3N4-SiC试样中的Si3N4分解较多,SiC-Si3 N4-Si试样的表面和内部都明显含有单质Si,SiC-Si3N4-SiO2试样表面区域的Si2N2O晶体发育很好,而内部区域的晶体发育较小.     

Selective laser reaction synthesis of SiC,Si3N4 and HfC/SiC composites for additive manufacturing

Selective laser reaction sintering techniques (SLRS) techniques were investigated for the production of near net-shape non-oxide ceramics including SiC, Si₃N₄, and HfC/SiC composites that might be compatible with prevailing powder bed fusion additive manufacturing processes. Reaction bonded layers of covalent ceramics were produced using in-situ reactions that occur during selective laser processing and layer formation. During SLRS, precursor materials composed of metal and/or metal oxide powders were fashioned into powder beds for conversion to non-oxide ceramic layers. Laser-processing was used to initiate simultaneous chemical conversion and local interparticle bonding of precursor particles in 100 vol% CH₄ or NH₃ gases. Several factors related to the reaction synthesis process—precursor chemistry, gas-solid and gas-liquid synthesis mechanisms, precursor vapor pressures—were investigated in relation to resulting microstructures and non-oxide yields. Results indicated that the volumetric changes which occurred during in-situ conversion of single component precursors negatively impacted the surface layer microstructure. To circumvent the internal stresses and cracking that accompanied the conversion of Si or Hf (that expands upon conversion) or SiO_x (that contracts during conversion), optimized ratios of the precursor constituents were used to produce near isovolumetric conversion to the product phase. Phase characterization indicated that precipitation of SiC from the Si/SiO₂ melt formed continuous, crack-free, and dense layers of 93.7 wt% SiC that were approximately 35 µm thick_, while sintered HfC/SiC composites (84.2 wt% yield) were produced from the laser-processing of Hf/SiO₂ in CH₄. By contrast, the SLRS of Si/SiO_x precursor materials used to produce Si₃N₄ resulted in whisker formation and materials vaporization due to the high temperatures required for conversion. The results demonstrate that under appropriate processing conditions and precursor selection, the formation of near net-shape SiC and SiC composites might be achieved through single-step AM-compatible techniques.     

Formation mechanisms of Si3N4 microstructures during silicon powder nitridation

Silicon nitride (Si₃N₄) was synthesized under a nitrogen gas flow (100 mL/min) using a molten salt nitriding method to investigate the effects of the temperature and NaCl content on the α-Si₃N₄ content in products and their micro-morphologies. Adding NaCl and β-Si₃N₄ in silicon powders resulted in Si nitridation products divided into two layers. Analysis of the lower product using X-ray diffraction revealed a change in the α-Si₃N₄ content with changes in the temperature and NaCl content. Analysis of the lower and upper layers using scanning electron microscopy revealed that the upper layer contained Si₃N₄ nanowires, Si₃N₄ nanobelts, and clastic oxide impurities; the lower one contained short needle-like and blocky Si₃N₄. From the microstructures of the products, the product morphology related to that the dry mixing procedure did not correspond to homogenization of the starting Si-Si₃N₄-NaCl mixtures and the different concentrations of raw materials resulted in different morphologies.     

氮化硅增强石英陶瓷天线罩复合材料的研究

通过对氮化硅，石英复合材料体系的研究，探讨了氮化硅含量对材料性能及其物相组成的影响；在该体系中引入氮化硼后，复合材料的强度和抗热震性能得到提高。     

Effects of different types of sintering additives and post-heat treatment (PHT) on the mechanical properties of SHS-fabricated Si3N4 ceramics

Porous silicon nitride (Si₃N₄) ceramics were fabricated by self-propagating high temperature synthesis (SHS) using Si, Si₃N₄ and sintering additive as raw materials. Effects of different types of sintering additives with varied ionic radius (La₂O₃, Sm₂O₃, Y₂O₃, and Lu₂O₃) on the phase compositions, development of Si₃N₄ grains and flexural strength (especially high-temperature flexural strength) were researched. Si₃N₄ ceramics doped with sintering additive of higher ionic radius had higher average aspect ratio, improved room-temperature flexural strength but degraded high-temperature flexural strength. Besides, post-heat treatment (PHT) was conducted to crystallize amorphous grain boundary phase thus improving the creep resistance and high-temperature flexural strength of SHS-fabricated Si₃N₄ ceramics. Excellent high-temperature flexural strength of 140 MPa~159 MPa and improved strength retention were achieved after PHT at 1400 °C.     

Grain growth kinetics in microwave sintered graphene platelets reinforced ZrO2/Al2O3 composites

The grain growth kinetics and mechanical properties of graphene platelets(GPLs) reinforced ZrO₂/Al₂O₃(ZTA) composites prepared by microwave sintering were investigated. The calculated grain growth kinetics exponent n indicated that the GPLs could accelerate the process of the Al₂O₃ columnar crystal growth. And the grain growth activation energy of the Al₂O₃ columnar crystal indicated that the grain growth activation energy of the GPLs doped ZTA composites is much higher than those of pure Al₂O₃ and ZTA in microwave sintering. The optimal mechanical properties were achieved with 0.4?vol% GPLs, whose relative density, Vickers hardness and fracture toughness were 98.76%, 18.10?GPa and 8.86?MPa?m^1/2, respectively. The toughening mechanisms were crack deflection, bridging, branching and pull-out of GPLs. The results suggested that GPLs-doped are good for the Al₂O₃ columnar crystal growth in the ZTA ceramic and have a potentially improvement for the fracture toughness of the ceramics.     

Al和Si对MgO-Si3 N4复合材料强度和显微结构的影响

以电熔镁砂、氮化硅与Al或Si为原料,制备的试样经1400℃烧后制成了MgO-Si3N4复合材料,研究了金属Al或Si对MgO-Si3N4复合材料强度的影响.发现Al或Si的加入均可显著提高MgO-Si3N4复合材料的常温耐压强度和高温抗折强度(1400℃).然后借助SEM和EDAX等手段研究了加入4%Al或Si的MgO-Si3N4复合材料的显微结构,揭示了金属Al和Si的增强作用机理体系中的Al转化为晶须状的氮氧化物,起纤维增韧作用;体系中的Si转化为粒状或絮状的氮化硅,起颗粒增强作用.     

氧化烧结Si3N4-SiC复合材料的性能研究

采用工业级SiC(0.043～1.1mm段砂)和10μm的Si3N4粉,按照SiC与Si3N4的质量比为90:10配料,在玛瑙研钵中混合均匀,然后加入PVA结合剂,采用20MPa压力压制成不同尺寸的试样,于110℃恒温干燥箱内干燥24h后,按照规定的烧成制度处理。对氧化气氛下烧结的Si3N4-SiC复合材料进行了常(高)温强度、抗氧化性能、抗热震性能、抗侵蚀性能的研究,并利用XRD和SEM对试样进行了物相和显微结构分析。结果表明:试样的高温(1400℃)强度略高于其常温强度;试样具有较好的抗氧化性,在1000℃氧化60h后,其面质量增加仅为0.32mg.cm-2;试样经1200℃空冷至20℃的强度保持率达75%,具有较好的抗热震性能;氧化烧结制备的Si3N4-SiC坩埚在1000℃空气中,经20h冰晶石熔体侵蚀处理后,坩埚内壁仅有少量侵蚀,具有较好的抗冰晶石熔体侵蚀性能;坩埚在空气中经1150℃20h铜熔体侵蚀处理后,受到严重侵蚀,但在埋炭条件下处理时,坩埚没有受到侵蚀。     

Effects of N2 pressure and Si particle size on mechanical properties of porous Si3N4 ceramics prepared via SHS

Porous silicon nitride ceramics with high flexural strength and high porosity were directly fabricated by self-propagating high temperature synthesis (SHS). The effects of N₂ pressure and Si particle size on the phase composition, microstructure, and mechanical property were investigated. N₂ influences not only the thermodynamics but also the kinetics of the SHS as initial reactant. Flexural strength ranged between 67 MPa and 134 MPa with increasing N₂ pressure. On the other hand, flexural strength ranged from 213 MPa to 102 MPa with different Si particle sizes. This plays an important role on the final diameter and length of β-Si₃N₄ grains and the formation mechanism of porous Si₃N₄ ceramics.     

SiC含量对反应烧结SiC-Si3N4复合材料性能的影响

以粒度均≤0.044mm的工业Si粉和α-SiC粉为原料,酚醛树脂为结合剂(占总粉末质量的6.5%),配成SiC含量(质量分数)分别为10%、30%、50%和70%的4组试样,经200MPa冷等静压成型后,在N2气氛中(压力为1.25MPa)于1395℃反应烧结制备了SiC-Si3N4复合材料,并采用SEM、XRD和EDS等测试手段对试样进行了观察和测试。结果表明:随着粉料中SiC含量的增加,烧后试样的体积密度下降,显气孔率提高,抗折强度降低,以SiC加入量为10%的试样性能最优;4组试样经800℃～室温空冷热震15次后的抗折强度保持率均在90%以上,表明材料具有良好的抗热震性能。     

Preparation of high-strength Si3N4 antenna window using selective laser sintering

In this study, a high-strength silicon nitride (Si₃N₄) antenna window was successfully developed via selective laser sintering (SLS) with cold isostatic pressing (CIP) after debinding before final sintering. The effects of CIP after debinding and sintering aids on the bulk density, total porosity, bending strength and microstructure of Si₃N₄ ceramics were examined. The results show that the bending strength of SLS Si₃N₄ ceramics can be greatly improved by adding sintering aids between Si₃N₄ granules and by CIP after debinding. Optimal performance of ceramics is obtained by CIP after debinding and the use of inter-granule sintering aids. The porosity, bulk density, and bending strength are 18.7%, 3.11 g/cm³, and 685 MPa, respectively. Eliminating the pores by the CIP after debinding and by inter-granule sintering aids promotes the growth of rod-like β-Si₃N₄, which lock with each other contribute to the strengthening of Si₃N₄ ceramics.     

Evolution of microstructure and properties of Si3N4 whisker reinforced composites during densification by polymer infiltration and pyrolysis

Si₃N₄ whisker (Si₃N_4w) reinforced composites were prepared by a near-net shaping process, i.e., gel-casting of the Si₃N_4w preform followed by polymer infiltration and pyrolysis (PIP) densification using polysilazane as precursor. The densification process by PIP was described mathematically, after which several key parameters affecting densification efficiency were discussed. The small pore size (0.04 ～ 1 μm) of Si₃N_4w preform can cause filtration effect (low permeability of precursor with a molecular size bigger than pore size), which resulted in the density gradient of the composites. Porosity (P) dependence of flexural strength and elastic modulus of Si₃N_4w/Si₃N₄ followed a power law of (1 – P). With increasing density, the response of Si₃N_4w when confronting cracks transformed from whisker debonding to whisker fracture, which was supposed to be due to the increase of whisker/matrix interface strength. The Si₃N_4w/Si₃N₄ developed by us achieved a good balance between high strength and low dielectric constant, making it promising for high-temperature wave-transparent application.     

氮化硅及其微粉的制备

本文介绍了氮化硅的性能、应用范围以及其微粉的制备方法。     

氮化硅及其微粉的制备

介绍了氮化硅的性能、应用范围以及其微粉的制备方法。