Low-temperature preparation of Si3N4/SiC porous ceramics via foam-gelcasting and microwave-assisted catalytic nitridation

Si₃N₄/SiC porous ceramics were fabricated by a novel foam-gelcasting and microwave-assisted catalytic nitridation method at a temperature as low as 1273?K for 60?min or after only 10?min at 1373?K utilizing commercial Si and SiC with trace of impurity Fe (0.33?wt%) as starting materials. The Si₃N₄/SiC porous ceramics containing porosity of 68.54?±?0.73% which were fabricated at 1373?K for 10?min had flexural and compressive strengths of 5.28?±?0.17?MPa and 12.86?±?1.55?MPa.     

High temperature mechanical properties of porous Si3N4 prepared via SRBSN

The high temperature strength and fracture behavior of porous Si₃N₄ ceramics prepared via reaction bonded Si₃N₄ (RBSN) and sintered reaction bonded Si₃N₄ (SRBSN) were investigated at 800–1400?°C. The weight gain after oxidation for 15?min and the microstructure of the edge and center of the fracture surface clearly show that the internal oxidation of porous SRBSN is unavoidable with porosity of ~ 50% and mean pore size of 700?nm. The oxidation of Si₃N₄ and intergranular Y₂Si₃O₃N₄ phase may responsible for the high temperature strength degradation of SRBSN. Porous Si₃N₄ ceramics prepared with addition of 1?wt% C showed low strength degradation at temperature >?1200?°C.     

A non-sintering fabrication method for porous Si3N4 ceramics via sol hydrothermal process

A non-sintering fabrication method for porous Si₃N₄ ceramics with high porosity and high mechanical strength was proposed. Strength of the porous ceramics can be obtained by silica sol mass transfer process in hydrothermal conditions rather than a traditionally controlled high temperature sintering process. Under hydrothermal circumstances, silica sol is continuously transferred to the necks of Si₄N₃ powder compact, depositing there and thus consolidating the ceramic skeleton. The key of the method to obtain homogeneous microstructure and mechanical strength is how to keep the silica sol from gelatin during hydrothermal procedure. The stabilization of silica sol and its affecting factors were studied. The results indicated that ultrasonic treatment makes alkali-catalyzed silica sol remain stable even in 200?℃ hydrothermal condition, which insures consecutive silica transportation. The effect of hydrothermal time on open porosity/mechanical strength of the porous Si₄N₃ ceramics were also thoroughly investigated. The porous Si₄N₃ ceramics with open porosity above 42% and flexural strength of 45?MPa were obtained without any high temperature sintering process. This method can be widely employed for the preparation of other porous ceramics as well.     

Fabrication and properties of Si3N4 bioscaffolds with orderly–interconnected big pore channels and well–distributed small pores

This paper focuses on investigating the technical potential for fabricating porous ceramic bioscaffolds for the repair of osseous defects from trauma or disease by inverse replication of three–dimensional (3–D) printed polymer template. Si₃N₄ ceramics with pore structure comprising orderly–interconnected big pore channels and well–distributed small pores are successfully fabricated by a technique combining 3–D printing, vacuum suction filtration and oxidation sintering. The Si₃N₄ ceramics fabricated from the Si₃N₄ powder with addition of 10?wt% talcum by sintering at 1250?°C for 2?h have little deformation, uniform microstructure, low linear shrinkage of 4.1%, high open porosity of 58.2%, relatively high compression strength of 6.4?MPa, orderly–interconnected big pore channels and well–distributed small pores, which are promising bioscaffold in the field of bone tissue engineering.     

Dielectric and mechanical properties of porous Si3N4 ceramics prepared via low temperature sintering

Borophosphosilicate bonded porous silicon nitride (Si₃N₄) ceramics were fabricated in air using a conventional ceramic process. The porous Si₃N₄ ceramics sintered at 1000–1200 °C shows a relatively high flexural strength and good dielectric properties. The influence of the sintering temperature and contents of additives on the flexural strength and dielectric properties of porous Si₃N₄ ceramics were investigated. Porous Si₃N₄ ceramics with a porosity of 30–55%, flexural strength of 40–130 MPa, as well as low dielectric constant of 3.5–4.6 were obtained.     

Porous Si3N4/SiC Ceramics Prepared via Nitridation of Si Powder with SiC Addition

Porous Si₃N₄/SiC ceramics with high porosity were prepared via nitridation of Si powder, using SiC as the second phase and Y₂O₃ as sintering additive. With increasing SiC addition, porous Si₃N₄/SiC ceramics showed high porosity, low flexural strength, and decreased grain size. However, the sample with 20wt% SiC addition showed highest flexural strength and lowest porosity. Porous Si₃N₄/SiC ceramics with a porosity of 36–45% and a flexural strength of 107‐46MPa were obtained. The linear shrinkage of all porous Si₃N₄/SiC ceramics is below 0.42%. This study reveals that the nitridation route is a promising way to prepare porous Si₃N₄/SiC ceramics with favorable flexural strength, high porosity, and low linear shrinkage.     

Preparation and characterization of porous Si3N4-bonded SiC ceramics and morphology change mechanism of Si3N4 whiskers

Porous Si₃N₄-bonded SiC ceramics with high porosity were prepared by the reaction-sintering method. In this process, Si₃N₄ was synthesized by the nitridation of silicon powder. The X-ray diffraction (XRD) indicated that the main phases of the porous Si₃N₄-bonded SiC ceramics were SiC, α-Si₃N₄, and β-Si₃N₄, respectively. The contents of β-Si₃N₄ were increased following the sintering temperature. The morphology of Si₃N₄ whiskers was investigated by scanning electron microscope (SEM), which was shown that the needle-like (low sintering-temperature) and rod-like (higher sintering-temperature) whiskers were formed, respectively. From low to high synthesized temperature, the highest porosity of the porous Si₃N₄ bonded SiC ceramic was up to 46.7%, and the bending strength was ~11.6?MPa. The α-Si₃N₄ whiskers were derived from the reaction between N₂ and Si powders, the growth mechanism was proved by Vapor–Solid (VS). Meanwhile, the growth mechanism of β-Si₃N₄ was in accordance with Vapor–Solid–Liquid (VSL) growth mechanism. With the increase of sintering temperature, Si powders were melted to liquid silicon and the α-Si₃N₄ was dissolved into the liquid then the β-Si₃N₄ was precipitated successfully.     

Enhanced high-temperature dielectric properties and microwave absorption of SiC nanofibers modified Si3N4 ceramics within the gigahertz range

Si₃N₄ ceramics modified with SiC nanofibers were prepared by gel casting aiming to enhance the dielectric and microwave absorption properties at temperatures ranging from 25?°C to 800?°C within X-band (8.2–12.4?GHz). The results indicate that the complex permittivity and dielectric loss are significantly increased with increased weight fraction of SiC nanofibers in the Si₃N₄ ceramics. Meanwhile, both complex permittivity and dielectric loss of SiC nanofibers modified Si₃N₄ ceramics are obviously temperature-dependent, and increase with the higher test temperatures. Increased charges mobility along conducting paths made of self-interconnected SiC nanofibers together with multi-scale net-shaped structure composed of SiC nanofibers, Si₃N₄ grains and micro-pores are the main reason for these enhancements in dielectric properties. Moreover, the calculated microwave absorption demonstrates that much enhanced microwave attenuation abilities can be achieved in the SiC nanofibers modified Si₃N₄ ceramics, and temperature has positive effects on the microwave absorption performance. The SiC nanofibers modified Si₃N₄ ceramics will be promising candidates as microwave absorbing materials for high-temperature applications.     

Neural network modeling and analysis of gel casting preparation of porous Si3N4 ceramics

Based on orthogonal experimental results of porous Si₃N₄ ceramics by gel casting preparation, a three-layer back propagation artificial neural network (BP ANN) was developed for predicting the performances of porous Si₃N₄ ceramics. The results indicated that BP ANN was a very useful and accurate tool for the prediction and optimization of porous Si₃N₄ ceramics performances. By using the developed ANN model, the influences of the compositions on performances of porous Si₃N₄ ceramics were investigated, and some important conclusions were drawn as follows: for the flexural strength of Si₃N₄ ceramics, solid loading has an optimum value where can achieve a maximum value, and the optimum solid loading decreases with the increase of monomer content; the porosity of sintering body monotonically decreases with the increase of solid loading, and it increases with monomer content; the porosity of sintering body monotonically increases with the increase of the ratio of crosslinking agent to monomer.     

A novel aerogels/porous Si3N4 ceramics composite with high strength and improved thermal insulation property

A novel ZrO₂-SiO₂ aerogels/porous Si₃N₄ ceramics composite with high strength, low density, good dielectric properties and low thermal conductivity was synthesized by filling ZrO₂-SiO₂ aerogels into the porous Si₃N₄ ceramics through vacuum sol-impregnating. The effects of aerogels on the microstructure and properties of composite were discussed. The results show that aerogels could form a mesoporous structure and significantly decrease the thermal conductivity from 9.8 to 7.3 W m^?1 K^?1. Meanwhile, the density, mechanical and dielectric properties of the porous Si₃N₄ ceramics could not be affected after introducing ZrO₂-SiO₂ aerogels. The composite exhibits high porosity (62.6%), high flexural strength (53.86 MPa) and low dielectric constant (2.86). The ZrO₂-SiO₂ aerogels/porous Si₃N₄ ceramics composite shows great potential as radome materials applied in the fields of aerospace.     

Fabrication and properties of porous Si3N4 ceramics by aqueous gelcasting using low-toxic DMAA gelling agent

A low-toxic and water-soluble monomer N, N-dimethylacrylamide (DMAA) was employed as a gelling agent in the gelcasting of porous Si₃N₄ ceramics. The process conditions and composition for slurry preparation (with a solid loading of 36?vol%), the consolidation and sintering of green bodies were investigated and optimized. The effects of various factors such as zeta potential, pH value of the premix solution, dispersant dosage and ball milling time on the rheological properties of the slurries were investigated. The results suggest that the best rheological properties (66.5 mPa.s at a shear rate of 96.3?s^?1) of the slurries were obtained when pH value ranged between 9 and 11, dispersant dosage reached 1?wt%, and ball milling time was 6?h. All the as-prepared green bodies showed a homogeneous microstructure and high flexural strength ≥ 26?MPa with a maximum up to 46.3?MPa when the ratio of DMAA to MBAM, initiator dosage, polymerization temperature and time were 14, 1?wt%, 70?°C and 90?min, respectively. The sintered bodies had a homogeneous microstructure, excellent and regulatable properties, a flexural strength of 216.3–327.3?MPa, and a porosity of 39.6–29.1% by varying the sintering temperature from 1710?°C to 1810?°C and the holding time from 1?h to 3?h. The superior comprehensive effect makes DMAA a promising candidate for an environmentally friendly gelling agent in gelcasting of porous Si₃N₄ ceramics.     

Novel porous Si3N4 ceramics prepared by aqueous gelcasting using Si3N4 poly-hollow microspheres as pore-forming agent

In this paper, novel porous Si₃N₄ ceramics were prepared by aqueous gelcasting using Si₃N₄ poly-hollow microspheres as pore-forming agent. The effect of Si₃N₄ poly-hollow microsphere content on the phase composition, microstructure, shrinkage, porosity and mechanical properties of the prepared porous Si₃N₄ ceramics were investigated. It is found that there is only β-Si₃N₄ phase in all the prepared porous Si₃N₄ ceramics. Meanwhile, the SEM results show that the pores in the porous Si₃N₄ ceramics distribute uniformly, the added Si₃N₄ poly-hollow microspheres and the basal body contact closely. With the increase of Si₃N₄ poly-hollow microsphere content, the shrinkage of the porous Si₃N₄ ceramics decreases gradually, and the porosity of the porous Si₃N₄ ceramics decreases firstly and then increases. Furthermore, the flexural strength and fracture toughness of the porous Si₃N₄ ceramics decrease with the increase of the Si₃N₄ poly-hollow microsphere content.     

Porous Si3N4 ceramics prepared by aqueous gelcasting using low–toxicity DMAA system: Regulatable microstructure and properties by monomer content

In this study, the low–toxicity monomer N, N–dimethylacrylamide (DMAA), serving as both gelling agent and pore–forming agent, was adopted to fabricate porous Si₃N₄ ceramics with a regulatable microstructure and property by aqueous gelcasting. Results indicate that monomer content played an important role in regulating and optimizing the properties of sintered bodies. With increasing monomer content (5.94–30.69?wt%), both slurry viscosity (maximum 0.14?Pa?s at 95.40 s^?1) and green body strength (11.35–49.23?MPa) exhibited monotonic increasing trends, demonstrating superior mechanical properties to those obtained using the neurovirulent acrylamide (AM) gelling system. The increased monomer content not only improved porosity, but also promoted α→β–Si₃N₄ transformation as well as β–Si₃N₄ grain growth through enhancing the connectivity of interlocking pores and accelerating the vapor phase transport during liquid–phase sintering. These variations in phase composition and microstructure derived from the varied monomer content further resulted in monotonic changes in porosity (40.32–51.50%), mean pore size (0.27–0.38?μm), flexural strength (202.77–132.15?MPa), fracture toughness (2.93–2.32?MPa?m^1/2), dielectric constant (3.48–2.78) and loss (3.52–3.09?×?10^?3) at 10?GHz for sintered bodies, displaying an excellent comprehensive properties. This study suggests a promising prospect for DMAA in preparation of high–performance porous Si₃N₄ ceramics by aqueous gelcasting.     

Pore structure control of Si3N4 ceramics based on particle-stabilized foams

Porous Si₃N₄ ceramics with open, closed pores and nest-like structures were prepared by direct foaming method, and the stability of bubbles and the microstructures of sintered Si₃N₄ foam ceramics were investigated. The bubbles produced by short-chain amphiphiles have higher stability as compared with that produced by long-chain surfactants. Si₃N₄ ceramic foams using short-chain amphiphiles are particle-stabilized one, porous Si₃N₄ ceramics with open and closed pores can be easily prepared with this method, and the nest-like microstructure in Si₃N₄ foam ceramics is achieved at high gas-pressure sintering conditions. The decrease of flexural strength due to the increase of porosity can be weakened by decreasing pore size.     

Enhancement of thermal shock resistance in β-Si3N4 coating with in situ synthesized β-Si3N4 nanowires/nanobelts on porous Si3N4 ceramics

A dense β-Si₃N₄ coating toughened by β-Si₃N₄ nanowires/nanobelts was prepared by a combined technique involving chemical vapor deposition and reactive melt infiltration to protect porous Si₃N₄ ceramics in this work. A porous β-Si₃N₄ nanowires/nanobelts layer was synthesized in situ on porous Si₃N₄ ceramics by chemical vapor deposition, and then Y–Si–Al–O–N silicate liquid was infiltrated into the porous layer by reactive melt infiltration to form a dense composite coating. The coating consisted of well-dispersion β-Si₃N₄ nanowires/nanobelts, fine β-Si₃N₄ particles and small amount of silicate glass. The testing results revealed that as-prepared coating displayed a relatively high fracture toughness, which was up to 7.9 ± 0.05 MPa m^1/2, and it is of great significance to improve thermal shock resistance of the coating. After thermal cycling for 15 times at ΔT = 1200 °C, the coated porous Si₃N₄ ceramics still had a high residual strength ratio of 82.2%, and its water absorption increased only to 6.21% from 3.47%. The results will be a solid foundation for the application of the coating in long-period extreme high temperature environment.     

Joining of Si3N4/Si3N4 with in-situ formed Si-Al-Yb oxynitride glasses interlayer

Si₃N₄ ceramic was successfully joined to itself with in-situ formed Yb-Si-Al oxynitride glass interlayer. The joints were composed of three parts: (I) Si₃N₄ matrix, (II) oxynitride glass interlayer in which hexagonal or fine elongated β-sialon grains and a few ball-like β-Si₃N₄ grains exist, and (III) diffusion zone in Si₃N₄ matrix containing a thin dark layer and a ~ 25?µm thick bright layer. The seam owned similar microstructure to matrix and was inosculated with the matrix as a whole. The strength of the joint tended to increase with the increase of bonding temperature and reached the value of 225?MPa, when the joints were prepared at 1600?°C for 30?min under a pressure of 1.5?MPa. The high-temperature strength remained 94.7% and 75.2% of R.T. strength when the joints were tested at 1000?°C and 1200?°C, respectively. It may be contributed to the high softening temperature of the Yb-Si-Al oxynitride glass phase formed in the seam. Even suffered to the air exposure for 10?h at 1200?°C, the residual strength of the joints was still 143?MPa, attributed to the existence of YbAG phase.     

Self-propagating high temperature synthesis (SHS) of porous Si3N4-based ceramics with considerable dimensions and study on mechanical properties and oxidation behavior

The aim of present work is to fabricate porous Si₃N₄ ceramics with considerable dimensions and homogeneous microstructure by self-propagating high temperature synthesis (SHS) using Si, Si₃N₄ diluent and Y₂O₃ as raw materials. The results indicate that Si₃N₄ diluent with coarse particle sizes and appropriate β-phase content is beneficial to obtain porous Si₃N₄ ceramics with homogeneous microstructure and excellent mechanical property by controlling the shrinkage inside the sample. The produced Si₃N₄ ceramics possessed excellent flexural strength of 168 MPa～259 MPa, and high Weibull modulus of 11.0～17.2. Additionally, BN and SiC are added as second phase to modify the properties of Si₃N₄-based ceramics. Optimum flexural strength of 170 MPa and 137 MPa were obtained with 10 wt.% addition of BN and SiC respectively. After oxidation at 1100 °C～1300 °C, second phase-doped Si₃N₄ ceramics also presented higher residual strength than pure Si₃N₄ ceramics.     

Effect of the molecular weight and concentration of PEG solution on microstructure and mechanical properties of Si3N4 ceramics fabricated by gel-casting

Gel-casting is a promising preparation technology of Si₃N₄ structural ceramics. The process involves drying of the “green” gel-cast parts before densification. And the drying of green gel-cast bodies is an important step in the gel-casting manufacturing process. In this work, the Si₃N₄ gel-cast green bodies were dried in polyethylene glycol (PEG) solution with the purpose of obtaining Si₃N₄ ceramics with good mechanical properties. The effect of the molecular weight and concentration of PEG solution on drying rate, microstructure and mechanical properties of Si₃N₄ ceramics was studied. The results indicated that with the increase of molecular weight of PEG, the drying rate increased obviously and the structure became more uniform and dense when the concentration of solution was 20?wt%. The Si₃N₄ ceramics after sintering have the excellent flexural strength (662.6?MPa) under PEG600 drying condition. Furthermore, the concentration of PEG600 solution had a positive effect on drying and sintering of the green body. Therefore, the bending strength reached 871.1?MPa under 65?wt% PEG 600 solution drying condition. Overall, the drying process (drying in 65?wt% PEG600 solution) promotes the efficiency and quality of drying of Si₃N₄ gel-cast green bodies, which is beneficial for the subsequent drying and sintering process.     

Thermal and mechanical properties of Si3N4 ceramics obtained via two-step sintering

Si₃N₄ ceramics were prepared using novel two-step sintering method by mixing α-Si₃N₄ as raw material with nanoscale Y₂O₃–MgO via Y(NO₃)₃ and Mg(NO₃)₂ solutions. Si₃N₄ composite powders with in situ uniformly distributed Y₂O₃–MgO were obtained through solid–liquid (SL) mixing route. Two-step sintering method consisted of pre-deoxidization at low temperature via volatilization of in situ-formed MgSiO₃ and densification at high temperature. Variations in O, Y, and Mg contents in Si₃N₄–Y₂O₃–MgO during first sintering step are discussed. O and Mg contents decreased with increasing temperature because SiO₂ on Si₃N₄ surface reacted with MgO to form low-melting-point MgSiO₃ compound, which is prone to volatilize at high temperature. By contrast, Y content hardly changed due to high-temperature stability of Y–Si–O–N quaternary compound. In the second sintering step, skeleton body was densified, and the formation of Y₂Si₃O₃N₄ secondary phase occurred simultaneously. Two-step sintered Si₃N₄ ceramics had lower total oxygen content (1.85 wt%) than one-step sintered Si₃N₄ ceramics (2.51 wt%). Therefore, flexural strength (812 MPa), thermal conductivity (92.1 W/m·K), and fracture toughness (7.6 MPa?m^1/2) of Si₃N₄ ceramics prepared via two-step sintering increased by 28.7%, 16.9%, and 31.6%, respectively, compared with those of one-step sintered Si₃N₄ ceramics.     

Fabrication and wear behaviors of graded Si3N4 ceramics by the combination of two-step sintering and β-Si3N4 seeds

Graded Si₃N₄ ceramics with sandwich-like microstructure were fabricated by the combination of hot-pressing, spark plasma sintering and β-Si₃N₄ seeds. Phase compositions, microstructures, mechanical properties, and wear behaviors were investigated. Main α-Si₃N₄ phase were detected in the outer layers, and only β-Si₃N₄ phase were observed in the inner layers. The outer layer with ultra-fine equiaxed grains were well bonded to the inner layer with a distinct bimodal grain size distribution. Vickers hardness of outer layer (～21.2?GPa) was much higher than that of inner layer (～16.1?GPa), whereas fracture toughness of outer layer (～3.5?MPa?m^1/2) was much lower than that of inner layer (～5.9?MPa?m^1/2), indicative of the hard surface and tough core. Due to the ultra-fine microstructure and high hardness of outer layer, the graded Si₃N₄ ceramics exhibited superior wear resistance with low wear rate.