Mechanical properties and microstructure of porous BN–SiO2–Si3N4 composite ceramics

Porous silicon nitride (Si₃N₄) ceramics incorporated with hexagonal boron nitride (h-BN) and silica (SiO₂) nanoparticles were fabricated by pressureless-sintering at relatively low temperature, in which stearic acid was used as pore-making agent. Bending strength at room and high temperatures, thermal shock resistance, fracture toughness, elastic modulus, porosity and microstructure were investigated in detail. The mechanical properties and thermal shock resistance behavior of porous Si₃N₄ ceramics were greatly influenced by incorporation of BN and SiO₂ nanoparticles. Porous BN–SiO₂–Si₃N₄ composites were successfully obtained with good critical thermal shock temperature of 800 °C, high bending strength (130 MPa at room temperature and 60 MPa at 1000 °C) and high porosity.     

Effect of BN content on microstructures,mechanical and dielectric properties of porous BN/Si3N4 composite ceramics prepared by gel casting

Porous BN/Si₃N₄ composite ceramics with different BN contents have been fabricated by gel casting. The rheological behaviors of the suspensions, microstructure, mechanical properties, dielectric properties and critical temperature difference of thermal shock (ΔT_C) of porous BN/Si₃N₄ composite ceramics with different BN contents were investigated. With BN contents increasing, the mechanical properties of the porous BN/Si₃N₄ composite ceramics were partially declined, but the dielectric properties and thermal shock resistances were enhanced at the same time. For the porous Si₃N₄ ceramic without BN addition, the porosity, flexural strength, dielectric constant and critical temperature difference were 48.1%, 128 MPa, 4.1 and 395 °C, while for the 10 vol% BN/Si₃N₄ porous composite ceramics, they were 49.4%, 106.6 MPa, 3.8, and 445 °C, respectively. The overall performance of the obtained porous BN/Si₃N₄ composite ceramics indicated that it could be one of the ideal candidates for high-temperature wave-transparent applications.     

Influence of hBN content on mechanical and tribological properties of Si3N4/BN ceramic composites

Silicon nitride materials containing 1–5 wt% of hexagonal boron nitride (micro-sized or nano-sized) were prepared by hot-isostatic pressing at 1700 °C for 3 h. Effect of hBN content on microstructure, mechanical and tribological properties has been investigated. As expected, the increase of hBN content resulted in a sharp decrease of hardness, elastic modulus and bending strength of Si₃N₄/BN composites. In addition, the fracture toughness of Si₃N₄/micro BN composites was enhanced comparing to monolithic Si₃N₄ because of toughening mechanisms in the form of crack deflection, crack branching and pullout of large BN platelets. The friction coefficient was not influenced by BN addition to Si₃N₄/BN ceramics. An improvement of wear resistance (one order of magnitude) was observed when the micro hBN powder was added to Si₃N₄ matrix. Mechanical wear (micro-failure) and humidity-driven tribochemical reaction were found as main wear mechanisms in all studied materials.     

Sintering behavior of ZrB2–SiC composites doped with Si3N4: A fractographical approach

ZrB₂–SiC composite ceramics were doped with 0, 1, 3 and 5 wt% Si₃N₄ plus 1.6 wt% carbon (pyrolized phenolic resin) as sintering aids and fabricated by hot pressing process under a relatively low pressure of 10 MPa at 1900 °C for 2 h. For a comparative study, similar ceramic compositions were also prepared by pressureless sintering route in the same processing conditions, with no applied external pressure. The effect of silicon nitride dopant on the microstructural evolution and sintering process of such ceramic composites was investigated by a fractographical approach as well as a thermodynamical analysis. The relative density increased by the addition of Si₃N₄ in hot pressed samples as a fully dense composite was achieved by adding 5 wt% silicon nitride. A reverse trend was observed in pressureless sintered composites and the relative density values decreased by further addition of Si₃N₄, due to the formation of gaseous products which resulted in the entrapment of more porosities in the final structure. The formation of ZrC phases in pressureless sintered samples and layered BN structures in hot pressed ceramics was detected by HRXRD method and discussed by fractographical SEM-EDS as well as thermodynamical analyses.     

Enhanced dielectric permittivity and thermal conductivity of hexagonal boron nitride/poly(arylene ether nitrile) composites through magnetic alignment and mussel inspired co-modification

In this work, we present novel hexagonal boron nitride (h-BN)/poly(arylene ether nitrile) nanocomposites with high dielectric permittivity and thermal conductivity. For this purpose, the interfacial adhesion and orientation of nanofillers are the two key factors that need to be considered. Firstly, iron oxide was attached onto the surface of h-BN to obtain magnetically responsive property, which would realize the orientation of h-BN by applying an external magnetic field during the preparation process of PEN composites. Secondly, the magnetic h-BN was further modified by mussel-inspired method with dopamine and secondary functional monomer (KH550). It was found that the alignment of h-BN and improvement of interfacial adhesion resulted in the interesting properties of PEN composites. With addition of 30 wt% modified h-BN, the dielectric permittivity of PEN composites was increased from 3.2 of neat PEN to 16.4 (increased by 413%), and the low dielectric loss was remained. Meanwhile, the thermal conductivity was enhanced to 0.662 W/m K (increased by 140%) at the same loading content. In addition, the resulting h-BN/PEN nanocomposites maintained high mechanical strength and thermal stability even the nanofillers loading content reached 30 wt%. Therefore, the dielectric and thermally conductive h-BN/PEN composites with high mechanical strength and thermal stability have big advantages in the area of energy storage devices.     

In-situ reaction synthesis of porous Si2N2O-Si3N4 multiphase ceramics with low dielectric constant via silica poly-hollow microspheres

In the present work, a novel and facile process has been proposed to fabricate porous Si₂N₂O-Si₃N₄ multiphase ceramics with low dielectric constant (ε_r＜4.0). Since silica poly-hollow microspheres could serve as the source of SiO₂ and the pore-forming agent, they have been introduced into Si₃N₄ slurry through the gelcasting technique. This process is benefited from the liquid phase sintering reaction between SiO₂ and Si₃N₄ with the aid of sintering additives, leading to in-situ synthesis of Si₂N₂O phase and porous structure. The content of silica poly-hollow microspheres has great influence on the properties of the final products. It indicates that Si₂N₂O phase would become the major phase when the content of silica poly-hollow microspheres was above 25 wt%. Furthermore, the micromorphology results reveal that the content of pores with many smaller aggregate microspheres increases as microspheres amount rises. As a result, along with the addition of silica poly-hollow microspheres, the bulk density decreases to 1.32±0.01 g/cm³, and open porosity ranges from 28.4±0.4% to 52.0±0.5%. Porous Si₂N₂O-Si₃N₄ multiphase ceramics prepared with 25 wt% silica poly-hollow microspheres addition possess flexural strength of 42.3±3.8 MPa, low dielectric constant of 3.31 and loss tangent of 1.93×10⁻³. It turns out to be an effective method to fabricate porous Si₂N₂O-Si₃N₄ composites with excellent mechanical and dielectric properties, which could be applied to radome materials.     

Fabrication of surface-treated BN/ETDS composites for enhanced thermal and mechanical properties

The ceramic/polymer composites based on epoxy-terminated dimethylsiloxane (ETDS) and boron nitride (BN) were prepared for use as thermal interface materials (TIMs). 250 µm-sized BN was used as a filler to achieve high-thermal-conductivity composites. To improve the interfacial adhesion between the BN particles and the ETDS matrix, the surface of BN particles were modified with silica via the sol–gel method with tetraethyl orthosilicate (TEOS). The interfacial adhesion properties of the composites were determined by the surface free energy of the particles using a contact angle test. The surface-modified BN/ETDS composites exhibited thermal conductivities ranging from 0.2 W/m K to 3.1 W/m K, exceeding those of raw BN/ETDS composites at the same weight fractions. Agari׳s model was used to analyze the measured thermal conductivity as a function of the SiO₂-BN concentration. Moreover, the storage modulus of the BN/ETDS composites was found to increase with surface modification of the BN particles.     

Mechanical and dielectric properties of porous Si2N2O–Si3N4 in situ composites

Mechanical and dielectric properties of porous Si₂N₂O–Si₃N₄ in situ composites fabricated for use as radome by gel-casting process were investigated. The flexural strength of the Si₂N₂O–Si₃N₄ ceramics is 230.46 ± 13.24 MPa, the complex permittivity of the composites varies from 4.34 to 4.59 and the dissipation factor varies from 0.00053 to 0.00092 from room temperature to elevated temperature (1150 °C) at the X-band. In the porous regions, some Si₂N₂O fibers (50–100 nm in diameter) are observed which may improve the materials properties.     

Effect of the Y2O3 additive concentration on the properties of a silicon nitride ceramic substrate

Silicon nitride (Si₃N₄) ceramics offer excellent thermal, mechanical and dielectric properties, which make Si₃N₄ a good candidate material for an application as electronic packaging material. For an application as a heat dissipation substrate, most studies focused on achieving a high thermal conductivity through long-time heat preservation and different kinds of heat treatments. Very few studies also considered the mechanical and dielectric properties. In addition, there have not been systematic researches about influence of additives concentration and type on the combination properties of Si₃N₄. Therefore, in this study, Si₃N₄ ceramic samples were prepared via hot pressing at 1800 °C with a relatively short heat preservation step (2 h), with different amounts of Y₂O₃ added as sintering additive. The effect of the initial concentration of the rare earth oxide on the chemical composition, microstructure, thermal conductivity, as well as the mechanical and dielectric properties of the Si₃N₄ ceramic samples was systematically studied.     

Effect of Si addition on the mechanical and thermal properties of sintered reaction bonded silicon nitride

Advanced silicon nitride (Si₃N₄) ceramics were fabricated using a mixture of Si₃N₄ and silicon (Si) powders via conventional processing and sintering method. These Si₃N₄ ceramics with sintering additives of ZrO₂ + Gd₂O₃ + MgO were sintered at 1800 °C and 0.1 MPa in N₂ atmosphere for 2 h. The effects of added Si content on density, phases, microstructure, flexural strength, and thermal conductivity of the sintered Si₃N₄ samples were investigated in this study. The results showed that with the increase of Si content added, the density of the samples decreased from 3.39 g/cm³ to 2.92 g/cm³ except for the sample without initial Si₃N₄ powder addition, while the thermal diffusivity of the samples decreased slightly. This study suggested that addition of Si powder, which varied from 0 to 100%, in the starting materials might provide a promising route to fabricate cost-effective Si₃N₄ ceramics with a good combination of mechanical and thermal properties.     

Nonoxide–boron nitride composites: in situ synthesis,microstructure and properties

Hexagonal graphitic boron nitride (h-BN) composites show excellent corrosion and thermal shock resistance, good mechanical tolerance and machinability, especially Si₃N₄–BN and Sialon–BN composites; they have already been used as break rings for horizontal continuous casting of steel. However, the strength of the conventionally processed BN composites were remarkably degraded by the addition of BN due to the poor densification behavior and the existence of large BN flakes or agglomerates of BN flakes that acted as fracture flaws. This means that BN dispersoids with fine particle size and homogeneous distribution are the key factors to obtain high strength composites. By in situ process, such microstructural features can be realized. In this work, by using the proposed in situ reactions, synthesis, microstructures and properties of various in situ nonoxide-boron nitride (Nobn) composites including SiC–BN, Si₃N₄–BN, AlN–BN, Sialon–BN and Alon–BN composites were investigated. For some Nobn composite systems, due to the large volume expansion during the reaction processes, near-net shape sintering can be realized. For example, the sintering shrinkage of AlN-30 vol.% BN was 3.1% and that of Alon-21 vol.% BN was 4.2%. This will be an advantage for the fabrication of large and complicated products.     

Improved thermal conductivity of sintered reaction-bonded silicon nitride using a BN/graphite powder bed

Sintered reaction-bonded silicon nitride (SRBSN) with improved thermal conductivity was achieved after the green compact of submicron Si powder containing 4.22 wt% impurity oxygen and Y₂O₃-MgO additives was nitrided at 1400 °C for 6 h and then post-sintered at 1900 °C for 12 h using a BN/graphite powder bed. During nitridation, the BN/10 wt% C powder bed altered the chemistry of secondary phase by promoting the removal of SiO₂, which led to the formation of larger, purer and more elongated Si₃N₄ grains in RBSN sample. Moreover, it also enhanced the elimination of SiO₂ and residual Y₂Si₃O₃N₄ secondary phase during post-sintering, and thus induced larger elongated grains, decreased lattice oxygen content and increased Si₃N₄-Si₃N₄ contiguity in final SRBSN product. These characteristics enabled SRBSN to obtain significant increase (∼40.7%) in thermal conductivity from 86 to 121 W ∙ m⁻¹ ∙ K⁻¹ without obvious decrease in electrical resistivity after the use of BN/graphite instead of BN as powder bed.     

Synthesis and properties of AlN/MAS/Si3N4 ternary glass-ceramic composites with in-situ grown rod-like β-Si3N4 crystals

The AlN/MAS/Si₃N₄ ternary composites with in-situ grown rod-like β-Si₃N₄ were obtained by a two-step sintering process. The microstructure analysis, compositional investigation as well as properties characterization have been systematically performed. The AlN/MAS/Si₃N₄ ternary composites can be densified at 1650 °C in nitrogen atmosphere. The in-situ grown rod-like β-Si₃N₄ grains are beneficial to the improvement of thermal, mechanical, and dielectric properties. The thermal conductivity of the composites was increased from 14.85 to 28.45 W/(m K) by incorporating 25 wt% α-Si₃N₄. The microstructural characterization shows that the in-situ growth of rod-like β-Si₃N₄ crystals leads to high thermal conductivity. The AlN/MAS/Si₃N₄ ternary composite with the highest thermal conductivity shows a low relative dielectric constant of 6.2, a low dielectric loss of 0.0017, a high bending strength of 325 MPa, a high fracture toughness of 4.1 MPa m^1/2, and a low thermal expansion coefficient (α_{25–300 °C}) of 5.11 × 10^?6/K. This ternary composite with excellent comprehensive performance is expected to be used in high-performance electronic packaging materials.     

Effects of MgO addition on the microwave dielectric properties of high thermal-conductive silicon nitride ceramics sintered with ytterbia as sintering additives

1 mol% of MgO was added together with 7 mol% of Yb₂O₃ as sintering additives to silicon nitride powder to fabricate advanced silicon nitride ceramics with both high thermal conductivity and low dielectric loss at 2 GHz. The mixed powder was CIPed at a pressure of 120 MPa and was gas-pressure sintered at 1900 °C to >98% of theoretical density. The sintered Si₃N₄ sample exhibited a high thermal conductivity of ～100 W m^?1 K^?1 and a loss tangent (tan δ) of ～4 × 10^?4, concurrently. The tan δ was further reduced by half after the heat treatment at 1300 °C for 24 h. The improvement in tan δ due to the annealing was explained from the point of crystallization of the intergranular glassy phase.     

Microstructure and mechanical properties of tantalum carbide ceramics: Effects of Si3N4 as sintering aid

Stoichiometric Tantalum carbide (TaC) ceramics were prepared by reaction spark plasma sintering using 0.333–2.50 mol% Si₃N₄ as sintering aid. Effects of the Si₃N₄ addition on densification, microstructure and mechanical properties of the TaC ceramics were investigated. Si₃N₄ reacted with TaC and tantalum oxides such as Ta₂O₅ to form a small concentration of tantalum silicides, SiC and SiO₂, with significant decrease in oxygen content in the consolidated TaC ceramics. Dense TaC ceramics having relative densities >97% could be obtained at 0.667% Si₃N₄ addition and above. Average grain size in the consolidated TaC ceramics decreased from 11 µm at 0.333 mol% Si₃N₄ to 4 µm at 2.50 mol% Si₃N₄ addition. The Young's modulus, Vickers hardness and flexural strength at room temperature of the TaC ceramic with 2.50 mol% Si₃N₄ addition was 508 GPa, 15.5 GPa and 605 MPa, respectively. A slight decrease in bending strength was observed at 1200 °C due to oxidation of the samples.     

Fabrication and mechanical properties of boron nitride nanotube reinforced silicon nitride ceramics

In this study, silicon nitride (Si₃N₄) ceramics added with and without boron nitride nanotubes (BNNTs) were fabricated by hot-pressing method. The influence of sintering temperature and BNNTs content on the microstructures and mechanical properties of Si₃N₄ ceramics were investigated. It was found that both flexural strength and fracture toughness of Si₃N₄ were improved when sintering temperature increases. Moreover, α-Si₃N₄ phase could transform into β-Si₃N₄ phase completely when sintering temperature rises to 1800 °C and above. BNNTs can enhance the fracture toughness of Si₃N₄ dramatically, which increases from 7.2 MPa m^1/2 (no BNNTs) to 10.4 MPa m^1/2 (0.8 wt% BNNTs). However, excessive addition of BNNTs would reduce the fracture toughness of Si₃N₄. Meanwhile, the flexural strength and relative density of Si₃N₄ decreased slightly when BNNTs were added. The related toughening mechanism was also discussed.     

Effects of heat treatment on mechanical and dielectric properties of 3D Si3N4f/BN/Si3N4 composites by CVI

In this study, three-dimensional silicon nitride fiber-reinforced silicon nitride matrix (3D Si₃N_4f/BN/Si₃N₄) composites with a boron nitride (BN) interphase were fabricated through chemical vapor infiltration. Through comparing the changes of microstructure, thermal residual stress, interface bonding state, and interface microstructure evolution of composites before and after heat treatment, the evolution of mechanical and dielectric properties of Si₃N_4f/BN/Si₃N₄ composites was analyzed. Flexural strength and fracture toughness of composites acquired the maximum values of 96 ± 5 MPa and 3.8 ± 0.1 MPa·m^1/2, respectively, after heat treatment at 800 °C; however, these values were maintained at 83 ± 6 MPa and 3.1 ± 0.2 MPa·m^1/2 after heat treatment at 1200 °C, respectively. The relatively low mechanical properties are mainly attributed to the strong interface bonding caused by interfacial diffusion of oxygen and subsequent interfacial reaction and generation of turbostratic BN interphase with relatively high fracture energy. Moreover, the Si₃N_4f/BN/Si₃N₄ composites also displayed moderate dielectric constant and dielectric loss fluctuating irregularly around 5.0 and 0.04 before and after heat treatment, respectively. They were mainly determined based on the intrinsic properties of materials system and complex microstructure of composites.     

Diamond dispersed Si3N4 composites obtained by pulsed electric current sintering

30 vol.% 2 and 30 μm diamond dispersed Si₃N₄ matrix composites were prepared by pulsed electric current sintering (PECS) for 4 min at 100 MPa in the 1550–1750 °C range. The densification behaviour, microstructure, Si₃N₄ phase transformation and stiffness of the composites were assessed, as well as the thermal stability of the dispersed diamond phase. Monolithic Si₃N₄ with 4 wt% Al₂O₃ and 5 wt% Y₂O₃ sintering additives was fully densified at 1550 °C for 4 min and 60 MPa. The densification and α to β-Si₃N₄ transformation were substantially suppressed upon adding 30 vol.% diamond particles. Diamond graphitisation in the Si₃N₄ matrix was closely correlated to the sintering temperature and grit size. The dispersed coarse grained diamonds significantly improved the fracture toughness of the diamond composite, whereas the Vickers hardness was comparable to that of the Si₃N₄ matrix ceramic. The Elastic modulus measurements were found to be an excellent tool to assess diamond graphitisation in a Si₃N₄ matrix.     

The Microstructure and thermal diffusivity of carbon nanostructures/Si3N4 composites processed using spark plasma sintering

Graphene nanoribbons (GNRs) were obtained by unzipping multiwall carbon nanotubes (MWCNTs). Three different silicon nitride-carbon nanostructures were prepared by spark plasma sintering (SPS): ceramic composites that contained 1 wt% carbon nanofibers (CNFs), 1 wt% MWCNTs and 1 wt% GNRs respectively. The α to β-Si₃N₄ transformation ratio and thermal diffusivity of GNR/Si₃N₄ composites were higher than both CNF/Si₃N₄ composites and MWCNT/Si₃N₄ composites. Furthermore, the higher thermal diffusivities of GNR/Si₃N₄ composites can primarily be attributed to the higher number of elongate β-Si₃N₄ grains.