h-BN/Si3N4陶瓷复合材料的断裂行为及断裂韧性

以亚微米级α-Si3N4和h-BN粉末为原料,Y2O3-Al2O3为助烧剂,采用热压烧结制备了h-BN/Si3N4陶瓷复合材料.研究3h-BN含量对h-BN/Si3N4陶瓷复合材料断裂韧性及其断裂行为的影响.结果表明:随着h-BN含量增加,柱状β-Si3N4晶粒的直径和长径比均下降;未加h-BN时,β-Si3N4陶瓷以沿晶断裂为主,添加体积含量为6%和8%的h-BN后,复合材料出现明显的沿晶和穿晶断裂,而添加10%h-BN的陶瓷复合材料则以沿晶断裂为主.随着h-BN含量增加,h-BN/Si3N4陶瓷复合材料的断裂韧性下降,但由于h-BN颗粒对裂纹扩展的影响,因而其下降程度不大.     

原位无压烧结制备Si2 N2O-Si3 N4复相陶瓷

以Y2O3和Al2O3陶瓷粉体作为烧结助剂,原位无压液相烧结制备Si3N4-Si2N2O复相陶瓷,Si2N2O相通过SiO2 Si3N4 2Si2N2O反应生成.生坯采用注凝成型制备,然后在1780℃保温2h烧结,烧结体基本由板条状的Si2N2O及长柱状的β-Si3N4晶粒构成.Si2N2O陶瓷相对于Si3N4陶瓷而言,具有优异的抗氧化性能,低的弹性模量,以及低的热膨胀系数,因此,Si2N2O-Si3N4复相陶瓷结合了两者的优异性能,并大大提高了材料的热冲击性,材料的热冲击温差即使达到1200℃,其残余强度基本上没有变化.     

仿生制备多孔氮化硅陶瓷

以松木炭化后形成的多孔木炭为模板,经Y2O3/SiO2混合溶胶浸渍生物碳模板形成Y2O3/SiO2/C复合体,在高压氮气氛下(0.6MPa),1600°C碳热还原氮化制备出牛物形态多孔氮化硅陶瓷.借助XRD、SEM研究了烧结助剂、烧结温度、反应时间和烧结气氛对烧结产物显微结构和晶相的影响,探讨了多孔Si3N4陶瓷的反应过程和机理.结果表明,多孔si3N4陶瓷是由主晶相β-Si3N4和少量晶间玻璃相YsSi4n4O14组成;多孔Si3N4不仅保留了松木的管胞结构,还在孔道中生长出纤维状形貌的β-Si3N4颗粒;Si3N4的反应烧结过程包括α-Si3N4的形成、晶形转变(α-β相变)和晶粒生长三个阶段.在1450°C烧结的机理是气-固和气-气反应机理,在1600°C通过液相烧结的溶解-沉淀机理形成纤维状的多孔Si3N4陶瓷.     

Y2O3对反应烧结制备Si3N4多孔陶瓷的影响

采用Si粉混合Si3N4粉反应烧结工艺方法制备Si3N4多孔陶瓷,研究了烧结助剂Y2O3对Si3N4多孔陶瓷的相组成、微观结构、显气孔率和强度的影响,结果表明:在高纯N2气氛,1350℃保温12h条件下,添加5% Y2O3(质量分数)的Si与Si3N4混合粉中粉体颗粒界面位置形成微晶中间相,使硅粉完全氮化并全部生成Si3N4,新生成的的Si3N4有效桥联原料中颗粒,使得多孔陶瓷在显气孔率略降的同时抗折强度由无烧结助剂时的28.1MPa提高到45.2 MPa.     

β-Si3N4单晶体的制备

在自增韧Si3N4陶瓷的烧结过程中,添加作为晶种的长柱状β-Si3N4单晶体对于改善陶瓷的强度和韧性是非常有效的。本研究旨在制备出长柱状β-Si3N4单晶体,并对其尺寸和形貌进行有效的控制。通过对87.3wt/α-SiN4 8.3wt/Y2O3 4.4wt/SiO2体系进行气压烧结,经去除掉玻璃相等漂洗工艺后,制得β-Si3N4单晶体,其直径为1－2μm、长度为4－6μm。同时对不同烧结工艺下制得的β-Si3N4单晶体的尺寸和工艺参数的关系进行了研究。     

大气中烧结多孔氮化硅的相变和氧化机理研究

以α—Si3N4为原料，分别以Y2O3-Al2O3和MgO-Al2O3-SiO2两个体系作为烧结助剂，在大气中对氮化硅坯体在1400～1550℃进行烧结。研究了烧结温度、烧结助剂体系对氮化硅的氧化程度、氧化产物的影响。结果表明，以MgO-Al2O3-SiO2作烧结助剂有利于α-Si3N4转变为β-Si3N4，且该烧结助剂体系的的抗氧化能力也明显优于Y2O3-Al2O3体系。氮化硅在不同温度烧结时形成的氧化产物不同。     

CVI制备Si3N4p/Si3N4透波材料表征与性能

以SiCl4-NH3-H2为反应体系，采用化学气相渗透（CVI）法制备Si3N4p／Si3N4透波材料．XRF测试表明试样主要含Si、N、O三种元素．XRD测试表明复合材料主要成分为α-Si3N4和非晶沉积物和非晶SiO2，并有微量的β-Si3N4和晶体Si，高温热处理可使非晶沉积物转变为α-Si3N4和β-Si3N4．SEM照片显示颗粒团间结合不够致密，残留气孔偏大．试样的弯曲强度最高为94MPa，介电常数为4．1-4．8．     

长柱状β-Si3N4晶粒与SiC晶须在层状Si3N4/BN复合材料中的作用

用SiC晶须和长柱状β－Si3N4对Si3N4/BN层状材料的基体层和分隔层进行了强化,轧膜工艺对SiC晶须和原料中存在的少量β－Si3N4晶粒有一定的定向作用,而基体层中定向分布的SiC晶须和长柱状的β－Si3N4晶粒对基体层的强讳论作用类似于块体材料,其抗弯强度和断裂韧性的提高幅度都大于50％,分隔层中β－Si3N4的定向度较差,但这利利于形成网状结构,在分隔层中起到骨架的作用,同时还可以增加裂纹的扩展长度,改善分隔层与基体层的界面结合状态,最终得到性能最佳的材料的成分为Si3N4 20wt%SiC晶须（基体层）,BN＋15vol%β-SiN4（分隔层）,其断裂功可达4820J／m2,抗弯强度仍可保持在650Mpa。β     

放电等离子快速烧结SiC晶须增强Si3N4BN层状复合材料

采用放电等离子烧结技术（SPS）快速烧结了SiC晶须增强的Si3N4/BN层状复合材料。利用SPS技术，在烧结温度为1650℃，保温15min的条件下，材料的密度可达3．18g/cm^3, 抗弯强度高达600MPa，断裂功达到3500J/m^2。研究表明；特殊的层状结构，SiC晶须的拔出与折断是材料断裂功提高的主要原因。X射线衍射及扫描电子显微镜研究表明：α-Si3N4已经在短短的烧结过程中全部转变成长柱状的β-Si3N4，并且长柱状的β-Si3N4和SiC晶须具有明显的织构。     

自蔓延燃烧合成β-Si3N4棒晶

采用自蔓延高温合成（SHS），在高压氮气中成功地合成了β－Si3N4棒晶，研究了中不同量Y2O3对自蔓延燃烧合成β－Si3N4棒晶长径比的影响。结果表明，Y2O3添加量有一个最佳范围，当Y2O3的添加量在2wt％－5wt％时，棒晶生长均匀，长径比约为8．通过铜坩埚吸热淬火的方法，观察到β－Si3N4棒晶不同生长阶段的显微形貌，从而推测其生长机理为VLS和VS两种机理协同作用的结果。本文对β－Si3N4棒晶生长的反应历程也进行了阐述。     

SiO2-Si3N4复合材料的力学性能及其增韧机理

采用热压工艺制备了ＳｉＯ２－Ｓｉ３Ｎ４复合材料，其抗弯强度和断裂韧性达到１４３ＭＰａ和１．７ＭＰａ．ｍ＾１／２，比基体ＳｉＯ２材料分别提高１０７％和７０％，复合材料改善是由于高弹性模量的Ｓｉ３Ｎ４引入以及ＳｉＯ２和Ｓｉ３Ｎ４热膨胀系数不匹配导致的残余应力。     

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。      

ZrO2 (Y2O3) 增韧的氮化硅烧结体的性能及相关系

在高温(1400℃) 超高压(4. 2GPa) 下制备Y₂O₃ 部分稳定的ZrO₂ 增韧的氮化硅烧结体, 通过XRD 及机械性能测试等方法分析ZrO₂ 的相结构, 研究氮化硅烧结体的增韧机理。结果表明, 烧结体中加入少量的铝粉, 可提高t2ZrO₂ 的相变能力, 达到利用部分稳定的ZrO₂ 增韧氮化硅烧结体的目的。稳定剂Y₂O₃ 在ZrO₂ 中含量小于2. 5mol% 时, t→m 相变量及断裂韧性随Y₂O₃ 含量增加而逐渐提高, 韧性提高来源于相变增韧和微裂纹增韧; Y₂O₃含量大于2. 5mol% 时, t 相接近100% , 韧性主要来源于相变增韧, 增韧效果随Y₂O₃ 含量增加而逐渐减弱。Y₂O₃ 作为良好的烧结助剂, 促进氮化硅烧结体在超高压下致密化, 烧结体的硬度随Y₂O₃ 含量增加逐渐提高。      

Microstructure and Toughness of Seeded Hot-Pressed Si3N4 Ceramics

Densification, phase transformation and fracture toughness were studied in hot-pressed Si_3N_4 seeded by in-houseproduced large, elongated β-Si_3N_4 seeds. A mixture of Y_2O_3-Al_2O_3 was used as the sintering aid. Concentration ofseeds were varied from 0 to 6 wt pct and the sintering time at 1700℃ was varied from 1 to 4 h. Maximum fracturetoughness of 9.0 MPam~(1/2) was measured in samples containing 5 wt pct seeds, hot pressed at 1700℃ for 4 h.     

Crystal chemistry of β-Si3N4 solid solutions containing metal oxides

Phase equilibrium diagrams of Si₃N₄-metal oxides systems were reviewed. It was found that the solid solubility limits of different metal oxides in β-Si₃N₄ depends on the size and charge of the metal elements. A misfit factor was suggested to present these variables numerically. For some compositions in the systems Si,Al/N,O, Si, Be/N,O, Si,Al,Be/N,O and Si,Be,Mg/N,O the misfit factors were computed and plotted against the solubility limits. It was found that substantial amount of foreign atoms can be accommodated in the β-Si₃N₄ lattice when the misfit factor is small. When the misfit factor becomes larger, only small amount of foreign atoms enter the lattice. The results suggested that this method can be used to estimate the solid solubility limits of one or more metal oxides and nitrides in β-Si₃N₄.     

Protein-repellent silicon nitride surfaces: UV-induced formation of oligoethylene oxide monolayers

The grafting of polymers and oligomers of ethylene oxide onto surfaces is widely used to prevent nonspecific adsorption of biological material on sensors and membrane surfaces. In this report, we show for the first time the robust covalent attachment of short oligoethylene oxide-terminated alkenes (CH(3)O(CH(2)CH(2)O)(3)(CH(2))(11)-(CH═CH(2)) [EO(3)] and CH(3)O(CH(2)CH(2)O)(6)(CH(2))(11)-(CH═CH(2)) [EO(6)]) from the reaction of alkenes onto silicon-rich silicon nitride surfaces at room temperature using UV light. Reflectometry is used to monitor in situ the nonspecific adsorption of bovine serum albumin (BSA) and fibrinogen (FIB) onto oligoethylene oxide coated silicon-rich silicon nitride surfaces (EO(n)-Si(x)N(4), x > 3) in comparison with plasma-oxidized silicon-rich silicon nitride surfaces (SiO(y)-Si(x)N(4)) and hexadecane-coated Si(x)N(4) surfaces (C(16)-Si(x)N(4)). A significant reduction in protein adsorption on EO(n)-Si(x)N(4) surfaces was achieved, adsorption onto EO(3)-Si(x)N(4) and EO(6)-Si(x)N(4) were 0.22 mg m(-2) and 0.08 mg m(-2), respectively. The performance of the obtained EO(3) and EO(6) layers is comparable to those of similar, highly protein-repellent monolayers formed on gold and silver surfaces. EO(6)-Si(x)N(4) surfaces prevented significantly the adsorption of BSA (0.08 mg m(-2)). Atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), X-ray reflectivity and static water contact angle measurements were employed to characterize the modified surfaces. In addition, the stability of EO(6)-Si(x)N(4) surfaces in phosphate-buffered saline solution (PBS) and alkaline condition (pH 10) was studied. Prolonged exposure of the surfaces to PBS solution for 1 week or alkaline condition for 2 h resulted in only minor degradation of the ethylene oxide moieties and no oxidation of the Si(x)N(4) substrates was observed. Highly stable antifouling coatings on Si(x)N(4) surfaces significantly broaden the application potential of silicon nitride-coated microdevices, and in particular of microfabricated filtration membranes.     

SiC_W含量对SiC_W/Si_3N_4复合陶瓷力学及高温微波性能影响

以α-Si_3N_4粉、β-SiC_W为原料,Al_2O_3、Y_2O_3为烧结助剂,采用凝胶注模工艺制备了SiC_W/Si_3N_4复合陶瓷材料,烧结温度为1 650℃,保温1.5h。研究了SiC_W加入含量对SiC_W/Si_3N_4复合陶瓷的微观结构、力学及常温/高温微波吸收性能的影响。结果表明:随着SiC_W含量的增加,SiC_W/Si_3N_4复合陶瓷的抗弯强度和断裂韧性都有先増后减的趋势,当含量为10wt%时,抗弯强度达到最大值505MPa,断裂韧性达9.515MPa·m1/2。常温介电常数在SiC_W含量为10wt%时,实部达最大值12,在12GHz最大吸收值为-21dB。高温介电常数随着SiC_W含量的增加有先增后减的趋势,在含量为10wt%时,实部达到最大值12.5。相比于纯Si_3N_4陶瓷,当SiC_W含量为10wt%时,SiC_W/Si_3N_4复合陶瓷在11.7GHz左右最大吸收可达-27dB,有效吸收频带(小于-5dB)为11.2~12.3GHz。     

Influence of Yag Concentration and Pressing Time on Wear of Si3N4 Based Ceramics

Strength of Materials - Abrasive wear resistance of Si3N4 strongly depends on its microstructure, in particular, grain morphology. In this work, the effects of β-content, β-Si3N4 grain...