加入纳米氮化硅对氮化硅陶瓷性能与结构影响

本文以亚微米级氮化硅为起始原料，加入纳米氮化硅来增强基体，添加氧化铝和氧化钇为烧结助剂，等静压成型，采用无压烧结的方式来制备具有优良性能的氮化硅陶瓷。主要研究了纳米氮化硅的分散；纳米氮化硅的加入量对氮化硅陶瓷力学性能的影响；纳米氮化硅的加入量对氮化硅陶瓷使用性能的影响；纳米氮化硅的加入量对氮化硅陶瓷显微结构的影响。研究结果表明：乙醇作为溶剂在分散介质为聚乙二醇的情况下，超声波震荡40分钟时，纳米氮化硅分散效果最好；随纳米氮化硅加入量的增加，显气孔率增加，吸水率增大；加入3wt％的纳米氮化硅时，试样的体积密度最大，抗弯强度、洛氏硬度、断裂韧性最好，具有较理想的显微结构。     

烧结温度对放电等离子烧结氮化硅陶瓷显微结构和力学性能的影响

以亚微米级氮化硅为原料、Al_2O_3–Y_2O_3为烧结助剂,利用放电等离子烧结(spark plasma sintering,SPS)烧结技术制备氮化硅陶瓷。用X射线衍射和扫描电子显微镜对试样的物相组成和显微结构进行分析,研究了烧结温度对氮化硅陶瓷力学性能和显微结构的影响。结果表明,采用SPS烧结技术可在较低温度下获得致密度较高、综合力学性能较好的β相氮化硅陶瓷。随着烧结温度的提高,样品致密度、抗弯强度、断裂韧性均不断增大,在1 550℃时,其抗弯强度和断裂韧性分别达到973.74 MPa和8.23 MPa?m1/2。在1 550℃以下,陶瓷样品中β相氮化硅含量可达到98%,显微结构均匀,晶粒发育良好、呈长柱状,晶间紧密连接,晶间气孔较少。继续升高温度,部分晶粒发生异常长大,产生了更多的显微孔洞,抗弯强度急剧下降。     

添加Mg-Al-Si体系烧结助剂的氮化硅陶瓷的无压烧结

以MgO-Al2O3-SiO2体系作为烧结助剂,研究了氮化硅陶瓷的无压烧结。着重考察了烧结温度、保温时间以及烧结助剂用量等工艺因素对氮化硅陶瓷材料力学性能和显微结构的影响,通过工艺调整来设计材料微观结构以提高材料的力学性能。在烧结助剂质量分数为3.2％的情况下,经1 780℃,3 h无压烧结,氮化硅大都呈现长柱状β-Si3N4晶粒,具有较大的长径比,显微结构均匀。样品的相对密度达99%,抗弯强度为956.8 MPa,硬度HRA为93,断裂韧性为6.1 MPa·m1/3。具有较大长径比晶粒构成的显微结构是该材料表现较高力学性能的原因。     

烧结工艺对β-氮化硅陶瓷的影响

以β-Si3N4粉末为原料,以YAG（钇铝石榴石）为烧结助剂,通过气氛压力烧结（GPS）制备出致密的β-氮化硅陶瓷材料,形成大小均匀的柱状颗粒和小球状颗粒复合显微结构,研究了烧结助剂质量分数、烧结温度以及保温时间对β-氮化硅陶瓷致密化程度及力学性能的影响.     

烧结助剂及增强相对氮化硅陶瓷材料性能的影响

氮化硅陶瓷基复合材料由于其优异的性能广泛运用于市场各领域.本文概述了制备氮化硅陶瓷基复合材料常用的几种烧结助剂和增强相,综述了烧结助剂对材料烧结过程的影响以及几种常用增强相的研究现状及增韧机理,最后对氮化硅陶瓷基复合材料未来的发展趋势和研究方向进行了总结与展望.     

烧结助剂(Y_2O_3、Al_2O_3、La_2O_3)对β-Si_3N_4自增韧陶瓷的性能研究

利用氮化硅陶瓷的自增韧技术,使用复合烧结助剂和在氮化硅基体中添加长柱状β-Si_3N_4晶种,制备高断裂韧性的氮化硅陶瓷。采用X射线衍射、扫描电镜、阿基米德法、三点抗弯曲强度、单边切口梁法等测试方法对陶瓷的组成、显微结构、显气孔率以及抗弯强度和断裂韧性等进行了分析与表征。首先研究了无压烧结制备氮化硅陶瓷过程中,烧结助剂(Y_2O_3、Al_2O_3)对其烧结性能和力学性能的影响,当Y_2O_3含量为8wt%,Al_2O_3含量为4wt%时,氮化硅陶瓷的相对密度达95%以上,抗弯强度为674MPa,断裂韧性为6.34MPa·m~(1/2)。再通过引入La_2O_3提高氮化硅晶粒的长径比,使氮化硅陶瓷的抗弯强度和断裂韧性分别达到686MPa和7.42MPa·m~(1/2)。通过无压烧结工艺,在1750℃制备了长柱状的β-Si_3N_4晶种,晶种的平均长度为2.82μm,平均粒径为0.6μm,平均长径比为4.7。笔者着重研究了晶种对氮化硅陶瓷烧结性能和力学性能的影响。在氮化硅陶瓷中加入晶种后,其烧结性能和抗弯强度略有降低,但断裂韧性却得到了很大的提高;且随着晶种添加量的增加,断裂韧性先升高再降低,掺入量为2wt%时断裂韧性达到最大(7.68MPa·m~(1/2)),提高了20%以上。     

自增韧氮化硅陶瓷的制备与性能研究

氮化硅陶瓷具有优异的物理机械性能和化学性能,被广泛应用于高温、化工、冶金、航空航天等领域。在结构陶瓷中氮化硅陶瓷虽具有相对较高的断裂韧性,但为了进一步拓宽氮化硅陶瓷的运用领域和提高其使用可靠性,改善其断裂韧性一直是该材料研究的重要课题。笔者通过利用氮化硅陶瓷的自增韧技术,使用复合烧结助剂和在氮化硅基体中添加长柱状β-Si_3N_4晶种,制备高断裂韧性的氮化硅陶瓷。采用X射线衍射、扫描电镜、阿基米德法、三点抗弯曲强度、单边切口梁法等测试方法对陶瓷的组成、显微结构、显气孔率以及抗弯强度和断裂韧性等进行了分析与表征。首先研究了无压烧结制备氮化硅陶瓷过程中,烧结助剂(Y_2O_3和Al_2O_3)对其烧结性能和力学性能的影响,当Y_2O_3含量为8wt%,Al_2O_3含量为4wt%时,氮化硅陶瓷的相对密度达95%以上,抗弯强度为674 MPa,断裂韧性为6.34 MPa·m~(1/2)。再通过引入La_2O_3提高氮化硅晶粒的长径比,使氮化硅陶瓷的抗弯强度和断裂韧性达到686 MPa和7.42 MPa·m~(1/2)。笔者通过无压烧结工艺,在1 750℃制备了长柱状的β-Si_3N_4晶种,晶种的平均长度为2.82μm,平均粒径为0.6μm,平均长径比为4.7,着重研究了晶种对氮化硅陶瓷烧结性能和力学性能的影响。氮化硅陶瓷中加入晶种后,其烧结性能和抗弯强度略有降低,但断裂韧性得到了很大的提高;且随着晶种添加量的增加,断裂韧性先升高再降低,掺杂量为2wt%时,断裂韧性达到最大(7.68 MPa·m~(1/2)),提高了20%以上。     

氮化硅陶瓷抗裂性的研究

讨论了工艺因素对氮化硅陶瓷结构、物理机械性能及其抗裂性的影响。查明，Al2O3 Y2O3复合烧结助剂及与其相配合的硅酸乙酯结合剂对氮化硅陶瓷强受和抗裂性变化有影响。证明用压痕法可以评定陶瓷的抗裂性。     

氮化硅陶瓷的低温常压烧结及其力学性能

本文采用氧化镁(MgO)和磷酸铝(AlPO4)为烧结助剂,利用常压烧结工艺于1600℃制备了以α相为主相的氮化硅( Si3N4)陶瓷材料.利用XRD和SEM等对其物相组成和显微结构进行了表征,并分析烧结助剂含量对材料致密度的影响,研究氮化硅陶瓷的致密度与其力学性能之间的关系.结果表明:当AlPO4含量为20wt％ ～ 30wt％时,氮化硅陶瓷的致密度可达90％以上,抗弯强度为250～320 MPa.AlPO4在Si3N4陶瓷烧结中对提高其致密度与力学性能起到了重要的作用.     

添加氧化镁及稀土氧化物的烧结氮化硅陶瓷

一种新的烧结氮化硅陶瓷 ,其制作方法是同时添加氧化镁 (ＭｇＯ)稀土氧化物 (ＲＯ)作为氮化硅陶瓷的烧结助剂 ,在 1 45 0℃ ,氧化镁 稀土氧化物就会与氮化硅粉末表面的二氧化硅反应生成大量硅酸盐液相 ,使氮化硅陶瓷致密。通过控制ＭｇＯ ＲＯ的组成和烧结工艺 ,可制取各种不同性能的烧结氮化硅陶瓷 ,满足不同用途的需求。用该法制得和烧结氮化硅陶瓷 ,可高效、经济地制造各种复杂形状的产品 ,如切削刀具、密封环、轴承、喷嘴及各种耐高温、耐磨损、耐腐蚀制品等添加氧化镁及稀土氧化物的烧结氮化硅陶瓷     

烧结助剂对多孔氮化硅陶瓷的力学性能及介电性能的影响

通过添加烧结助剂,采用常压烧结工艺制备出不同气孔率(19%～54%)的氮化硅陶瓷.采用Archimedes法、三点弯曲法和Vickers硬度测试法测量了材料的密度、气孔率、抗弯强度及硬度.用X射线衍射及扫描电镜检测了相组成和显微结构.用谐振腔法测试了氮化硅陶瓷在10.2 GHz的介电特性.结果表明:材料具有优良的介电性能.随着烧结助剂的减少,样品中气孔率增加,力学性能有所下降,介电常数和介电损耗降低.添加Lu2O3所制备的氮化硅陶瓷的力学性能和介电性能优于添加Eu2O3或Y2O3制备的氮化硅陶瓷.当气孔率高于50%时,多孔氮化硅陶瓷(添加入5%的Y2O3或Lu2O3,或Eu2O3,质量分数)的抗弯强度可达170 MPa,介电常数为3.0～3.2,介电损耗为0.000 6～0.002.     

无压烧结氮化硅陶瓷的物理性能研究

以α-Si₃N₄粉末为原料,Y₂O₃和MgAl₂O₄体系为烧结助剂,采用无压烧结方式,研究了烧结温度、保温时间、烧结助剂含量以及各组分配比对氮化硅致密化及力学性能的影响。结果表明:以Y₂O₃和MgAl₂O₄为烧结助剂体系,氮化硅陶瓷在烧结温度为1 600 ℃,保温时间为4 h,烧结助剂含量为12.5%(质量分数),Y₂O₃和MgAl₂O₄质量比为1∶1时,综合性能最好;氮化硅陶瓷显气孔率为0.21%,相对密度为98.10%,抗弯强度为598 MPa,维氏硬度为15.55 GPa。     

冰刀用高强韧Si3N4陶瓷的制备与性能研究

以α-Si₃N₄粉为原料,MgO-La₂O₃-Lu₂O₃为三元复合烧结助剂,采用气压烧结工艺制备Si₃N₄陶瓷条,研究烧结助剂及添加β-Si₃N₄增强相对Si₃N₄陶瓷微观结构及力学性能的影响。结果表明,三元复合烧结助剂促进了烧结的致密化,提高了材料的力学性能,在最高烧结温度1 750 ℃、复合烧结助剂添加量8%(质量分数)时,得到密度为3.172 8 g/cm³、维氏硬度达到15.85 GPa、断裂韧性和抗弯强度分别为9.69 MPa·m^1/2和1 029 MPa的冰刀用Si₃N₄陶瓷。添加β-Si₃N₄材料的断裂韧性得到提高,最高达到10.33 MPa·m^1/2。Si₃N₄陶瓷本身的高硬度与加入的稀土氧化物使得所制备冰刀的硬度与润滑性能得到提高,表面性能优良。     

无压烧结制备纳米复合碳化硅陶瓷

以水基喷雾造粒而成含5%(质量分数)纳米氮化钛(TiN)颗粒的碳化硅(SiC)造粒粉为原料,采用无压烧结制备纳米复合SiC陶瓷。分析了烧结温度及保温时间对复合陶瓷烧结特性与显微结构的影响规律。结果表明:采取二步烧结可以实现SiC陶瓷在晶粒不明显长大的前提下实现致密化,二步烧结,即先升温到1950℃保温15min后迅速降至1850℃烧结1h,制备的SiC陶瓷具有较高收缩率、较低质量损失以及较高的致密度;纳米TiN颗粒加入后能与基体(SiC,Al2O3)部分发生反应生成TiC和AlN,明显改善SiC陶瓷的烧结性能,获得等轴状、细晶显微结构和优越的力学性能。     

粒子弥散强化氮化硅基陶瓷

运用晶界工程理论，选择能形成高耐炎度晶界相的Ｙ２Ｏ３和Ｌａ２Ｏ３双稀土氧化物为Ｓｉ３Ｎ４陶瓷烧结助剂，材料具有优异的高温强度。第二相碳化硅粒子的引入有效地改善了氮化陶瓷的显微结构和力学性能。以无压烧结工艺制备的高性能α／β－Ｓｉａｌｏｎ复相陶瘊等在实际应用中获得良好效果。     

氮化铝陶瓷低温真空热压烧结研究

以自蔓延高温合成的AIN粉体为原料,Y2O3、Dy2O3、La2O3为添加剂,采用真空热压烧结工艺,实现了含有添加剂的AIN陶瓷体的低温烧结;研究了烧结温度对AIN烧结性能的影响。用XRD、SEM对AIN高压烧结体进行了表征。研究表明：粉体粒径、烧结工艺、烧结助剂对AIN陶瓷低温烧结真空热压烧结性能有很大影响;含烧结助剂的真空热压烧结能够有效降低AIN陶瓷的烧结温度并缩短烧结时间,使烧结体的结构致密。烧结温度1550℃条件下,真空热压烧结90min时,得到的AIN陶瓷的致密度最高。     

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.     

Porous Silicon Nitride Ceramics Prepared by Reduction–Nitridation of Silica

A new method for preparing porous silicon nitride ceramics with high porosity had been developed by carbothermal reduction of die-pressed green bodies composed of silicon dioxide, carbon, sintering additives, and seeds. The resultant porous silicon nitride ceramics showed fine microstructure and uniform pore structure. The influence of SiO₂ particle size and sintering process (sintering temperature and retaining time) on the microstructure of sintering bodies was analyzed. X-ray diffractometry demonstrated the formation of single-phase β-Si₃N₄ via the reaction between silicon dioxide and carbon at high temperature. SEM analysis showed that pores were formed by the banding up of rod-like β-Si₃N₄ grains. Porous Si₃N₄ ceramics with a porosity of 70–75%, and a strength of 5–8 MPa, were obtained.     

New method of free silicon determination in pressureless sintered silicon nitride by Raman spectroscopy and XRD

Formation of silicon affects different physical properties of silicon nitride ceramics. Decomposition of Si₃N₄ and formation of free Si are highly important processes and depend on many factors. The proposed method of combined nano-Raman spectroscopy and X-ray diffraction (XRD) allows quantitative analysis of Si in silicon nitride. Raman spectroscopy enables the determination of atomic bonds and rapid and easy identification of free silicon. Further analysis of the crystalline phases by XRD enables the calculation of the amount of free silicon. The proposed complex method allows the characterization of such complicated processes as silicon nitride decomposition, microstructure formation and, in particular, the formation of the nanoscale grain boundary phase because Si nanosized precipitates are the nucleants of secondary phases during crystallization. Strong 522.8 cm⁻¹ mode and 943.1–984.3 cm⁻¹ transverse optical modes of free Si were clearly observed in the investigated silicon nitride that was subjected to pressureless sintering at 1800 °C. Reported ceramics demonstrated typical microstructures with elongated grains and relatively high microhardness and Young's modulus. It was shown that the aspect ratio depended linearly on the microhardness and Young's modulus. High values of the Young's modulus (more than 290 GPa) and microhardness (more than 1800 HV) were shown for reported silicon nitride produced by hot pressing and pressureless sintering via cold isostatic pressing with a higher quantity of sintering agent. The features of molecular structure of the reported Si₃N₄ ceramics were clearly described and discussed in detail and were found to be in good agreement with the microstructure and phase composition of these ceramics.     

Effect of α-Si3N4 Particle Size on the Microstructural Evolution of Si3N4 Ceramics

The effects of initial particle size on the microstructure of silicon nitride ceramics produced by pressureless sintering have been investigated. The microstructures of the silicon nitride ceramics varied considerably with the size of the initial powder. With decreasing powder size, abnormal grain growth was enhanced, which resulted in significant bimodal distribution of grain size. The observed results are discussed in relation to the two-dimensional nucleation and growth theory for faceted crystals.