Layered Silicon Nitride-Based Composites with Discontinuous Boron Nitride Interlayers

The influence of a strong/weak interface ratio on the mechanical properties of Si₃N₄/BN-based layered composites was studied. The ratio was controlled by the number of BN spots between the adjacent Si₃N₄ layers. By increasing the BN interface area from 0% to 72%, fracture toughness increased from 7.7 to 10.9 MPa·m^1/2, and bending strength decreased from 1275 to 982 MPa. Fracture toughness was improved from 8.6 to 10.1 MPa·m^1/2 by additional heat treatment of samples containing 2 vol%β-Si₃N₄ seed particles. The bending strength of samples with 35% weak BN interfaces, measured perpendicular and parallel to layer alignment, was 1260 and 1240 MPa, respectively. This confirmed the two-directional isotropy of layered samples.     

BN基复合陶瓷致密化的主要障碍

本文对ＢＮ基复合陶瓷进行了热压和无压烧结试验,对烧结体的密度变化和显微结构进行了研究,分析了影响ＢＮ基复合致密化的主要因素,认为卡片房式结构是妨ＢＮ基复合陶瓷致密化的主要原因。热压过程中施加的压力足够大时,可以破坏这种卡片房式结构,使片状ＢＮ定向排列,因而能获得同致密度的ＢＮ基复合陶瓷,热压过程中若有液相出现,有利于片状ＢＮ定向排列,因而能促进ＢＮ基复合陶瓷的致密化。无压烧结因不能消除坯体中的卡片     

Mechanical Properties of Three-Layered Monolithic Silicon Nitride–Fibrous Silicon Nitride/Boron Nitride Monolith

A three-layered composite, composed of a strong outer layer (monolithic S₃N₄) and a tough inner layer (fibrous Si₃N₄/BN monolith), was fabricated by hot-pressing. For the inner layer, a Si₃N₄–polymer fiber made by extrusion was coated by dipping it into a 20 wt% BN-containing slurry. The three-layered composite exhibited excellent mechanical properties, including high strength, work of fracture, and crack resistance, because of the combination of a strong outer layer and a tough inner layer. In other words, the strong outer layer withheld the applied stress, while the tough inner layer promoted crack interactions through the weak BN cell boundaries. Also, the residual thermal stress on the surface due to the anisotropy in the coefficient of thermal expansion of BN affected a median/radial crack generation after indentation.     

BN-YAION复合陶瓷的烧结行为

对ＢＮ－ＹＡｌＯＮ复合陶瓷进行了热压和无压烧结试验,对烧结体的密度变化和显微结构进行了研究,分析了影响ＢＮ基复合陶瓷致密化的主要因素．认为卡片房式结构是妨碍ＢＮ基复合陶瓷致密化的主要原因．热压过程中施加的压力足够大时,可以破坏这种卡片房式结构,使片状ＢＮ定向排列,因而能获得高致密度的ＢＮ基复合陶瓷．热压过程中若有液相出现,有利于片状ＢＮ定向排列,因而能促进ＢＮ基复合陶瓷的致密化．无压烧结时因不能消除原有的卡片房式结构,故虽有液相出现,也难以获得高致密度的ＢＮ基复合陶瓷     

High-temperature carbothermal synthesis and characterization of graphite/h-BN bimaterials

Hexagonal boron nitride (h-BN) and graphite have similar crystal structures, comparable lattice parameters, and coefficients of thermal expansion, but vastly different electrical and thermal transport. Despite their key differences, it is possible to couple h-BN and graphite in a bimaterial system allowing the unique properties of both materials to be utilized in a single component. Through a carbothermal reduction of B₂O₃ in nitrogen, the surface of graphite can be converted to h-BN. This results in a layered system that is electrically insulating on the surface due to h-BN, and more compliant as well as conductive within the substrate due to the graphite structural body. We discuss the high-temperature synthesis and characterization of this layered material, focusing on the processing–microstructure relationship as well as the interface of graphite/h-BN to assess the chemical and mechanical adhesion of the layers, and to establish how such properties are contingent on the reacting phase of B₂O₃. This is achieved by investigating the origin of h-BN formation and the unwanted side reaction of boron carbide formation, through the evaluation of the thermochemistry and kinetics governing the carbothermic reactions. We establish that a reaction temperature and holding time of 1700°C for 18 h produced the thickest h-BN layers which exhibited the highest fracture toughness over all lower temperature synthesis conditions.     

Fabrication of high aspect ratio boron nitride nanotube–ZrB₂ composites and the effect of dispersion

Ultrahigh-temperature ceramics (UHTCs) exhibit remarkable hardness and resistance to oxidative ablation, making them suitable for use in hypersonic environments, such as hypersonic aircraft and space shuttles. However, their low fracture toughness limits their applications as engineering materials. In this study, zirconium diboride, an extremely hard and oxidation-resistant UHTC, was sintered with high aspect ratio boron nitride nanotubes (BNNTs) to improve the fracture toughness of UHTC. Although the high aspect ratio BNNTs tend to become entangled and are inefficient in improving the fracture toughness of the composite, the use of plasma functionalization can effectively disperse the BNNTs in UHTC, resulting in the increase in the fracture toughness of the UHTC composite.     

氧化物/BN可加工复相陶瓷的高温氧化行为及表面裂纹修复

研究了2种可加工复相陶瓷Al2O3／BN和Y-ZrO2／BN在不同温度下的氧化行为及其热处理损伤修复。结果表明：高温时Al2O3／BN表面氧化生成致密的硼酸铝(Al18B2O33)氧扩散障碍层,并且与基体形成强结合的梯度抗氧化涂层,阻止了氧气向材料内部的快速扩散,因而具有良好的自愈合抗氧化性。而Y-ZrO2／BN复相陶瓷由于不能形成有效的氧化屏蔽,抗氧化性较差。2种复相陶瓷在900℃热处理后,表面形成的液态B2O3膜使压痕裂纹均得到愈合,压痕强度从热处理前的162MPa(Al2O3／BN)和336MPa(Y-ZrO2／BN)分别增加到热处理后的406MPa和585MPa。但在1100℃热处理2h后,由于过度的氧化会使Y-ZrO2／BN失去裂纹愈合的效果,压痕强度迅速下降。     

可加工氮化硅/氮化硼复相陶瓷的制备

以硅(Si)粉、六方氮化硼(h-BN)为原料,在氮气(N2)中用燃烧合成(combustion synthesis,CS)气固反应法,原位生成可加工氮化硅/氮化硼(Si3N4/h-BN)复相陶瓷.考察了h-BN不同体积分数(下同)对Si3N4/h-BN复相陶瓷可加工性的影响.结果表明:在实验条件下,Si粉氮化完全,不存在残余的游离Si.Si3N4/h-BN复相陶瓷中以柱状β-Si3N4为主相,β-Si3N4晶粒之间为针状h-BN相.随着h-BN相含量的增加,Si3N4/h-BN复相陶瓷的可加工性提高,抗弯强度先减小后增加.h-BN含量为25%时,Si3N4/h-BN复相陶瓷的抗弯强度最低.     

Effect of BN content on the structural,mechanical, and dielectric properties of PDCs-SiCN(BN) composite ceramics

Hexagonal boron nitride (h-BN) with low dielectric loss and high temperature resistance opens up new opportunities for the preparation of polymer-derived SiCN ceramics (PDCs-SiCN ceramics) with excellent mechanical and dielectric properties. BN-containing polymer-derived SiCN composite ceramics (PDCs-SiCN(BN) composite ceramics) with different BN content were prepared via a pyrolysis process of ball-milling-blended Polyvinylsilazane/boron nitride (PVSZ/BN) precursors. BN is stably embedded in the SiCN tissue and tightly bound with it. The appropriate content of BN greatly improves the mechanical properties of PDCs-SiCN ceramics, as BN reduces the number of pores and prevents crack expansion. Additionally, BN is also beneficial in lowering the dielectric loss of PDCs-SiCN ceramics because of the weakened polarization relaxation behavior. PDCs-SiCN (BN) composite ceramics have optimal mechanical and dielectric properties when the BN content is 1 wt%. The flexural strength, flexural modulus and compression strength of PDCs-SiCN(BN) composite ceramics with 1 wt% BN doping content were 189.37 MPa, 46.38 GPa, and 399.02 MPa, respectively. Its average dielectric loss (tanδ_ε) at 12.4-18 GHz is 0.0049.     

纳米BN包覆的Al2O3复合粉的制备及其烧结性能研究

以尿素和硼酸为氮化硼源，利用氢气还原法在亚微米级氧化铝粉末表面均匀包覆一层纳米级BN，包裹层的厚度可通过BN含量来调节。当氮气压力为0.52-0.53MPa时，复合粉经1400℃至1600℃热处理，中间产物Al-O-B分解得到BN，同时BN由t(turbostratic)相转变为h(hexagonal)相。1500℃处理可得到包裹紧密的h-BN-Al2O3纳米复合粉。以氮经硅为烧结助剂，30％BN－Al2O3(in volume)复合粉在1700热压烧结即可得到几乎完全致密化的纳米复相陶瓷，表观气孔率接近于零。材料的抗弯强度为446MPa，可用硬质合金钻头轻易钻孔。     

烧结助剂含量对多孔Si3N4/BN复合陶瓷力学性能和介电性能的影响

以Si3N4和BN为原料,叔丁醇为溶剂,SiO2、Y2O3和Al2O3为烧结助剂,采用凝胶注模成型工艺制备具有高强度、低介电常数多孔Si3N4/BN复合陶瓷。研究了Y2O3和Al2O3含量对多孔陶瓷气孔率、孔径分布、物相组成、显微结构、抗弯强度和介电常数的影响。结果表明:通过调节Y2O3和Al2O3含量,多孔Si3N4/BN复合陶瓷的气孔率由55%增加到68%,气孔尺寸呈单峰分布,平均孔径为0.89～1.02μm;抗弯强度和相对介电常数随Y2O3和Al2O3含量的增加而单调增大,抗弯强度和相对介电常数的变化范围分别为29.9～60.9 MPa和2.30～2.85;通过调节Y2O3和Al2O3含量调控气孔率,能够获得介电性能和力学性能可调的高性能透波材料。     

Spark plasma sintering of boron nitride micron tubes reinforced boron carbide ceramics with excellent mechanical property

In this paper, the novel boron nitride micron tubes (BNMTs) were used to reinforce commercial boron carbide (B₄C) ceramics prepared via spark plasma sintering technology. The effects of the sintering parameters, sintering temperature, the holding time, and the BNMTs content on the microstructure and mechanical properties of B₄C/BNMTs composite ceramics were studied. The results indicated that adding a proper amount of BNMTs could inhibit the grain growth of B₄C and improve the fracture toughness of the B₄C/BNMTs composite ceramics. The prepared composite ceramic sample with 5 wt% BNMTs at 1850°C, 8 min and 30 MPa displayed the best mechanical properties. The relative density, hardness, fracture toughness, and bending strength of the samples were 99.7% ± .1%, 35.62 ± .43 GPa, 6.23 ± .2 MPa m^1/2, and 517 ± 7.8 MPa, respectively. Therein, the corresponding value of hardness, fracture toughness, and bending strength was increased by 10.3%, 43.59%, and 61.5%, respectively, than that of the B₄C/BNMTs composite ceramic without BNMTs. It was proved that the high interface binding energy and bridging effect between boron carbide and BNMTs were the toughening principle of BNMTs.     

AlN—BN复合陶瓷的介电性能

以ＡｌＮ－ＢＮ复合陶瓷为研究对象，着重探讨了ＡｌＮ－ＢＮ复合陶瓷的极化机理，应用基本的介电介质物理理论，结合ＡｌＮ－ＢＮ复合陶瓷组成和结构特点，研究了ＡｌＮ－ＢＮ复合陶瓷介电性能（介电常数，介电损耗角正切值）随测量温度，测量频率变化而发生变化的温度特性和频率特性。     

Preparation of Machinable B4C/BN Composites and Their Oxidation Resistances at High Temperature

采用热压烧结工艺制备单相 B4C 陶瓷、B4C/BN 微米复相陶瓷和 B4C/BN 纳米复相陶瓷。研究了其在 1 000～1 300 ℃的等温氧化性能,通过对氧化后试样表面的物相组成和显微结构的分析,探讨了氧化机理。结果表明：单相 B4C 陶瓷、B4C/BN 微米复相陶瓷和 B4C/BN 纳米复相陶瓷的高温抗氧化性能随氧化温度提高和氧化时间增加而逐渐降低,试样氧化过程中质量损失逐渐明显。对试样在不同氧化温度下得到的氧化曲线进行了线性拟合分析,试样在 1 000 ℃时抗氧化性能较好,但在 1 300 ℃时抗氧化性能较差。氧化后试样表面的物相组成主要为 B4C 相、h-BN 相,以及少量的B2O3 相和 Al4B2O9 或 Al18B4O33 相。氧化后试样表面存在一层厚度约为 100 μm 的氧化层,氧化层中存在许多微孔和少量玻璃相物质。氧化生成的 B2O3挥发是导致试样质量随着氧化温度和氧化时间增加而显著减少的主要原因。     

On the synthesis of lithium boron nitride (Li3BN2)

Li₃BN₂ is a known lithium ion conductor and has been predicted lately to be a high capacity cathode for Li-ion batteries (Németh, 2014) [4]. In this study, we have investigated the synthesis of Li₃BN₂ through reactions between Li₃N and h-BN powders. Effects of the reaction temperature, holding time and reaction atmosphere on the formation of Li₃BN₂ have been evaluated. Rietveld refinement of X-ray diffraction patterns of all powders has been performed to quantify the percentage of each phase. The results show that both the reaction temperature and holding time affect strongly the percentage of Li₃BN₂ in the reaction product. Furthermore, a trace amount of oxygen in the reaction atmosphere can negatively impact the purity of the reaction product because of the high affinity of Li₃BN₂ towards oxidation.     

Defect-induced electronic conduction of tBN thin films

Two kinds of turbostratic boron nitride (tBN) thin films were deposited by sputtering with pure Ar or N₂ plasma in an ultraclean vacuum chamber. Current–voltage (I–V) characteristics of Ti/tBN/Ti structures revealed that films deposited in Ar showed at least three-orders higher conductivity with strong temperature and electric field dependence compared with those deposited in pure N₂. The origin of the higher conductivity was confirmed to be the nonstoichiometry and higher defect density of the tBN films. On the other hand, films deposited in pure N₂ plasma showed the characteristics of intrinsic insulator even though the basal plane of tBN was oriented normal to the substrate, namely, parallel to the direction of electronic conduction.     

Dielectric properties of polymer-derived ceramic reinforced with boron nitride nanotubes

The electrical and dielectric properties of boron nitride nanotubes (BNNTs) reinforced ceramic composites using the polymer-derived ceramic (PDC) processing route were investigated in this work. The electrical resistivity of the pristine PDC increases from 10⁶ to 10⁸ Ω m after the addition of BNNTs. When the BNNT loading was increased to 5 wt%, the average real relative permittivity of the PDC decreased from 2.94 to 2.80, while the quality factor (Q) of the PDC increased from 134.40 to 176.77. The BNNTs can increase the Q factor of the PDC due to the reduction in the porosity cause by the introduction of the BNNTs. Further increasing the BNNT content decreases the real relative permittivity of the nanocomposites and increases the Q factor at high frequency. The average real relative permittivity decreases to 2.29, while the average Q factor increases to 208.60 when the BNNT content is increased to 30 wt%. The dielectric loss after the addition of high fraction of BNNTs can be explained by the Lorentz resonance relaxation process. Results of this work showed that PDC-BNNT nanocomposites are satisfactory electromagnetic transparent materials when the BNNT fraction is less than 10 wt%.     

In-situ X-ray observation of phase transformation of rhombohedral boron nitride under static high pressure and high temperature

In-situ X-ray diffraction study for phase transformation of rhombohedral boron nitride (rBN) to a denser phase was performed under static high pressure (HP) and high temperature (HT) up to 9 GPa and 1600 °C. It was found that the layer stacking sequence of rBN structure began to change at less than 1 GPa, and the phase transformation to wurtzite structure (wBN) was observed at 6–7 GPa and room temperature. After conversion to wBN, further transformation to the zincblend type cubic structure (cubic BN) at 8 GPa and 1400 °C was observed, which is quenchable and the P-T conditions yielding cBN form were similar to that from hexagonal boron nitride. The observed behavior of the phase transformation of rBN by using in-situ X-ray diffraction study is well consistent with the results obtained from the quenching experiment from HP/HT by using belt type HP apparatus.

No structural change was observed at 600°C isothermal compression up t0 8GPa, while wBN formation was observed at room temperature compression at 7 GPa. This variation of the transformation behavior under HT isothermal compression may essentially be caused by the reduction of shear stress which affects the rotation and/or slip of hexagonal plane of rBN under HP.     

Machinability of Silicon Nitride/Boron Nitride Nanocomposites

The machinability and deformation mechanism of Si₃N₄/BN nanocomposites were investigated in the present work. The fracture strength of Si₃N₄/BN microcomposites remarkably decreased with increased hexagonal graphitic boron nitride ( h -BN) content, although machinability was somewhat improved. However, the nanocomposites fabricated using the chemical method simultaneously had high fracture strength and good machinability. Hertzian contact tests were performed to clarify the deformation behavior by mechanical shock. As a result of this test, the damage of the monolithic Si₃N₄ and Si₃N₄/BN microcomposites indicated a classical Hertzian cone fracture and many large cracks, whereas the damage observed in the nanocomposites appeared to be quasi-plastic deformation.     

纳米复相结构陶瓷的原位反应合成

简要介绍了原位反应合成纳米复相陶瓷的原理及其可行性，认为此方法是制备纳米复相结构陶瓷的有效方法. 同时讨论了氮化硼(h-BN)复相陶瓷的特点及其性能改善的关键因素，认为采用传统方法难以获得高性能的BN复相陶瓷. 提出了一系列原位化学反应，并采用热压或无压烧结获得了细小而均匀分散的非氧化物?氮化硼(Nobn)复相陶瓷，纳米级的BN片晶主要分布在基体晶粒的晶界处，当BN体积含量适当时即可获得一种全新的部分弱晶界陶瓷复合材料(PWICs)，这种材料具有很好的综合力学性能.