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.     

Fabrication of Machinable Silicon Carbide-Boron Nitride Ceramic Nanocomposites

SiC/BN nanocomposite powders with the microstructure of micrometer-sized SiC particles coated with nanometer-sized BN particles were prepared via a chemical reaction, which used a mixture of boric acid (H₃BO₃) and urea (CO(NH₂)₂) as reactants coated on the surface of the SiC particles to react under a nitrogen-gas atmosphere. The results of XRD, TEM, and SAED studies showed that the coating layer (BN) was composed mostly of amorphous and nanometer-sized BN particles at the reaction temperature of 850°C. When the nanocomposite powders were hot-pressed at 1850°C, machinable SiC/BN ceramic nanocomposites with fine grain size and homogeneous microstructure were fabricated. The composite that contained 20 wt% BN exhibited high strength (the three-point bending strength was 588.4 ± 26.8 MPa) and excellent machinability.     

Control of Composition and Structure in Laminated Silicon Nitride/Boron Nitride Composites

Based on a biomimetic design, Si₃N₄/BN composites with laminated structures have been prepared and investigated through composition control and structure design. To further improve the mechanical properties of the composites, Si₃N₄ matrix layers were reinforced by SiC whiskers and BN separating layers were modified by adding Si₃N₄ or Al₂O₃. The results showed that the addition of SiC whiskers in the Si₃N₄ matrix layers could greatly improve the apparent fracture toughness (reaching 28.1 MPa·m^1/2), at the same time keeping the higher bending strength (reaching 651.5 MPa) of the composites. Additions of 50 wt% Al₂O₃ or 10 wt% Si₃N₄ to BN interfacial layers had a beneficial effect on the strength and toughness of the laminated Si₃N₄/BN composites. Through observation of microstructure by SEM, multilevel toughening mechanisms contributing to high toughness of the laminated Si₃N₄/BN composites were present as the first-level toughening mechanisms from BN interfacial layers as crack deflection, bifurcation, and pull-out of matrix sheets, and the secondary toughening mechanism from whiskers in matrix layers.     

Elevated-Temperature Mechanical Properties of Silicon Nitride/Boron Nitride Fibrous Monolithic Ceramics

A unique, all-ceramic material capable of nonbrittle fracture via crack deflection and delamination has been mechanically characterized from 25° through 1400°C. This material, fibrous monoliths, was comprised of unidirectionally aligned 250 μm diameter silicon nitride cells surrounded by 10 to 20 μm thick boron nitride cell boundaries. The average flexure strengths of fibrous monoliths were 510 and 290 MPa for specimens tested at room temperature and 1300°C, respectively. Crack deflection in the BN cell boundaries was observed at all temperatures. Characteristic flexural responses were observed at temperatures between 25° and 1400°C. Changes in the flexural response at different temperatures were attributed to changes in the physical properties of either the silicon nitride cells or boron nitride cell boundary.     

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.     

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.     

In Situ Reaction Synthesis of Silicon Carbide–Boron Nitride Composite from Silicon Nitride–Boron Oxide–Carbon

This work proposes a new approach, based on the reaction Si₃N₄+ 2B₂O₃+ 9C → 3SiC + 4BN + 6CO, to synthesize an SiC–BN composite. The composite was prepared by reactive hot pressing (RHP), at 2000°C for 60 min at 30 MPa under an argon atmosphere, following a 60 min hold at 1700°C without applied pressure before reaching the RHP temperature. TG-DTA results showed that a nitrogen atmosphere inhibited denitrification somewhat and retarded the reaction rate. The chemical composition of the obtained material was consistent with theoretical values. FE-SEM observation showed that in situ -formed SiC and BN phases were of spherical morphology with very fine particle size of ∼100 nm.     

Recent Advances in Boron Nitride Based Hybrid Polymer Nanocomposites

Boron nitride (BN) is an eminent inorganic compound having many interesting characteristics such as improved oxidation resistance, mechanical strength, good thermal conductivity (TC), higher bandgap, high chemical stability, thermal stability, high hydrophobicity, and electrical insulation. The use of BN as a filler in polymers is a well-established strategy to tailor the properties of polymer composites. Recent studies depict an interesting urge to reap the synergistic effect of various nanofillers with BN in the form of hybrids. Hence the consolidation of the works on BN based hybrid fillers would definitely attract researchers so that these new filler systems could be transformed into useful polymer nanocomposites in future. This review article focuses on the synthesis and characterization of various boron nitride based hybrids in detail. Moreover, the review also throws light on different BN hybrid reinforced polymer nanocomposites (PNCs) and their thermal, electrical, electronic as well as biomedical applications in a detailed manner. Thus the review anticipates serving as a tool toward understanding the recent trends in the field of boron nitride hybrid based ternary polymer composites.     

In Situ Reaction Synthesis of Silicon Carbide–Boron Nitride Composites

SiC–BN composites were prepared via the proposed in situ reaction, which used Si₃N₄, B₄C, and carbon as reactants. Adding SiC powder to the reactants controlled the BN content in the composite. For comparison, SiC–BN composites with the same phase compositions were produced via conventional processing. The in situ process was advantageous for obtaining better composites with fine grain size and homogeneous microstructures. The in situ composite that had a BN content of 53.71 vol% exhibited considerably high strength (342 MPa) and a very low elastic modulus (107 GPa). The SiC–25-vol%-BN in situ composite had a peak strength of 588 MPa, which was 95% of that of monolithic SiC; however, the elastic modulus was as low as half that of monolithic SiC. These in situ SiC–BN composites can be expected to have excellent thermal shock resistance and mechanical strain tolerance.     

Hot Isostatic Pressing of Silicon Nitride with Boron Nitride, Boron Carbide, and Carbon Additions

Si₃ N₄ test bars containing additions of BN, B₄C, and C, were hot isostatically pressed in Ta cladding at 1900° and 2050°C to 98.9% to 99.5% theoretical density. Room-temperature strength data on specimens containing 2 wt% BN and 0.5 wt% C were comparable to data obtained for Si₃ N₄ sintered with Y₂O₃, Y₂O₃ and Al₂O₃, or ZrO₂. The 1370°C strengths were less than those obtained for additions of Y₂O₃ or ZrO₂ but greater than those obtained from a combination of Y₂O₃ and Al₂O₃. Scanning electron microscope fractography indicated that, as with other types of Si₃N₄, roomtemperature strength was controlled by processing flaws. The decrease in strength at 1370°C was typical of Si₃N₄ having an amorphous grainboundary phase. The primary advantage of non-oxide additions appears to be in facilitating specimen removal from the Ta cladding.     

Fracture Toughness and Thermal Shock Behavior of Silicon Nitride–Boron Nitride Ceramics

Fracture toughness behavior, stress–strain behavior, and flaw resistance of pressureless-sintered Si₃N₄-BN ceramics are investigated. The results are discussed with respect to the reported thermal shock behavior of these composites. Although the materials behave linear-elastic and exhibit no R -curve behavior, their flaw resistance is different from that of other linear-elastic materials. Whereas the critical thermal shock temperature difference (Δ T _c) is enhanced by adding BN, the content of BN has no influence on the strength loss during severe thermal shocks.     

Thermogravimetry, Differential Thermal Analysis, and Mass Spectrometry Study of the Silicon Nitride–Boron Carbide–Carbon Reaction System for the Synthesis of Silicon Carbide–Boron Nitride Composites

Thermogravimetry, differential thermal analysis, mass spectrometry, and X-ray diffractometry were used to study the reaction process of the in situ reaction between Si₃N₄, B₄C, and carbon for the synthesis of silicon carbide–boron nitride composites. Atmospheres with a low partial pressure of nitrogen (for example argon + 5%–10% nitrogen) seemed to inhibit denitrification and also maintain a high reaction rate. However, the reaction rate decreased significantly in a pure nitrogen atmosphere. The experimental mass spectrometry results also revealed that B₄C in the Si₃N₄–B₄C–C system inhibited the reaction between Si₃N₄ and carbon and, even, the decomposition of Si₃N₄. The present results indicate that boron could be a composition stabilizer for ceramic materials in the Si-N-C system used at high temperature.     

Composition and Microstructure of Chemically Vapor-Deposited Boron Nitride, Aluminum Nitride, and Boron Nitride + Aluminum Nitride Composites

The composition and microstructure of dispersed-phase ceramic composites containing BN and AIN as well as BN and AIN single-phase ceramics prepared by chemical vapor deposition have been characterized using X-ray diffraction, scanning electron microscopy, electron microprobe, and transmission electron microscopy techniques. Under certain processing conditions, the codeposited coating microstructure consists of small single-crystal AIN fibers (whiskers) surrounded by a turbostratic BN matrix. Other processing conditions resulted in single-phase films of AIN with a fibrous structure. The compositions of the codeposits range from 2 to 50 mol% BN, 50 to 80 mol% AIN with 7% to 25% oxygen impurity as determined by electron microprobe analysis.     

Reaction-Bonded and Superplastically Sinter-Forged Silicon Nitride–Silicon Carbide Nanocomposites

Silicon nitride–silicon carbide (Si₃N₄–SiC) nanocomposites were fabricated by a process involving reaction bonding followed by superplastic sinter-forging. The nanocomposites exhibited an anisotropic microstructure, in which rod-shaped, micrometer-sized Si₃N₄ grains tended to align with their long axes along the material-flow direction. SiC particles, typically measuring several hundred nanometers, were located at the Si₃N₄ grain boundaries, and nanosized particles were dispersed inside the Si₃N₄ grains. A high bending strength of 1246 ± 119 MPa, as well as a high fracture toughness of 8.2 ± 0.9 MPa·m^1/2, was achieved when a stress was applied along the grain-alignment direction.     

Carbothermal Synthesis of Boron Nitride Coatings on Silicon Carbide

Pure BN coatings have been synthesized on the surface of SiC powders and fibers by a novel carbothermal nitridation method. Three stages are involved in the process: first, formation of a carbon layer on the SiC by the extraction of Si with chlorine; second, infiltration of the resulting nanoporous carbide-derived carbon (CDC) coating by a saturated boric acid solution; and finally, nitridation in ammonia at atmospheric pressure to produce the pure BN coating. X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and electron energy loss spectroscopy (EELS) were used to characterize the phase, elemental composition, and surface morphology of the coatings. The intermediate carbon layer acts as a template for BN growth, facilitates the formation of BN, and prevents the degradation of SiC fibers during nitridation. The whole process is simple, cost-effective, and less toxic due to the use of H₃BO₃ and NH₃ as precursors at atmospheric pressure compared with most commonly used chemical vapor deposition (CVD) methods. Uniform BN coatings obtained by this method prevent the bridging of fibers in the tow. The coating of powders is possible, which cannot be achieved by conventional CVD methods.     

Si3N4及其复合材料强韧化研究进展

简述了氮化硅陶瓷的结构、性能和制备工艺，并分别通过自增韧补强、纤维／晶须强韧化、层状结构强韧化、相变强韧化以及颗粒弥散强韧化等方法对氮化硅陶瓷的强韧化研究进行了分类叙述。     

Reactivity of Aluminum Nitride Powder in Aqueous Silicon Nitride and Silicon Carbide Slurries

The reactivity of AlN powder with water in supernatants obtained from centrifuged Si₃N₄ and SiC slurries was studied by monitoring the pH versus time. Various Si₃N₄ and SiC powders were used, which were fabricated by different production routes and had surfaces oxidized to different degrees. The reactivity of the AlN powder in the supernatants was found to depend strongly on the concentration of dissolved silica in these slurries relative to the surface area of the AlN powder in the slurry. The hydrolysis of AlN did not occur if the concentration of dissolved silica, with respect to the AlN powder surface, was high enough (1 mg SiO₂/(m² AlN powder)) to form a layer of aluminosilicates on the AlN powder surface. This assumption was verified by measuring the pH of more concentrated (31 vol%) Si₃N₄ and SiC suspensions also including 5 wt% of AlN powder (with respect to the solids).     

Boron Nitride Interphase in Ceramic-Matrix Composites

A BN interphase has been deposited, by isothermal/isobaric chemical vapor infiltration (ICVI) from BF₃─NH₃, within a preform made from ex-polycarbosilane (ex-PCS) fibers, at about 1000°C. In a second step, the BN-treated preform was densified with SiC deposited from CH₃SiCl₃─H₂ at about the same temperature. From a thermodynamic standpoint, ex-PCS fibers could be regarded as unreactive vs the BF₃─NH₃ gas phase assuming they are coated with a thin layer of carbon or/and silica. The as-deposited interphase consists of turbostratic BN (N/B < 1) containing oxygen. The SiC infiltration acts as an annealing treatment: (i) the BN interphase becomes almost stoichiometric and free of oxygen; (ii) the fibers undergo a decomposition process yielding a SiO₂/C layer at the BN/fiber interface. The weaker link in the interfacial sequence seems to be the BN/SiO₂ interface. Deflection of microcracks arising from the failure of the matrix takes place at (or nearby) that particular interface.     

High-Temperature Microstructure of a Hot-Pressed Silicon Nitride

The outstanding question as to the microstructure of silicon nitride at temperatures associated with potential high-temperature applications of the material is addressed experimentally by quenching thin (transmission electron microscopy) samples from 1450°C and examining them in the microscope. The morphology of the microstructure is qualitatively unchanged compared to the materials slowly cooled, for example, after hot-pressing, to room temperature. The most significant difference is that the thickness of the intergranular phase is larger, typically 2 to 10 nm, as compared to the ∼ 1 nm observed in the hot-pressed material. In addition there is an apparent increase in the volume fraction of the intergranular phase at the three-grain junctions. On the basis of a number of supporting experiments including both hot-stage transmission electron microscopy (up to 1000°C) and Auger electron spectroscopy of material fractured and examined at 850°C, the change in microstructure is concluded to occur at temperatures above about 1000°C.     

Microstructure of Silicon Carbide Whiskers Synthesized by Carbothermal Reduction of Silicon Nitride

The microstructure of silicon carbide whiskers synthesized by carbothermal reduction of silicon nitride has been studied using transmission electron microscopy. All of the whiskers examined are single crystals, and grow in the (111) crystallographic direction. Two different forms of stacking faults and microtwins were observed; in one the planar defects are normal to the whisker growth direction, and the other has the defect planes at an angle of about 70° to the growth axis, while both forms of the defects are on the [111] closed-packed planes. Without the addition of catalyst, droplets containing metallic impurities were not found at the tips of the whiskers synthesized by the present process. A core and outer regions were observed in the single-crystal whiskers, which may be evidence that the whiskers were formed by a two-stage mechanism.