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.     

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.     

Preparation,mechanical and thermal properties of Si3N4 ceramics by gelcasting using low–toxic DMAA gelling system and gas pressure sintering

In this work, Si₃N₄ ceramics were fabricated through an aqueous gelcasting method using a low–toxic monomer called N, N–dimethylacrylamide (DMAA) followed by gas pressure sintering at 1850 °C for 2 h under 6 MPa N₂ atmosphere. The effect of solid loading on performance of slurries, green and sintered bodies was investigated systematically. The results show that the slurries with a solid loading as high as 50 vol% (viscosity 0.17 Pa.s at 100 s^–1) were achieved. With the increase of solid loading (30–50 vol%), the green bodies exhibited a monotonically decreased, however high enough in general, flexural strength of 16.50–11.52 MPa, which was comparable to that of widely–used neurovirulent acrylamide (AM) gelling system. In regard to the sintered bodies, increasing solid loading significantly promoted sintering and improved mechanical properties and thermal conductivity as a result of the increased density, bimodal distribution structure, as well as suitable interfacial bonding strength. The best performance parameters of Si₃N₄ ceramics, bulk density of 3.25 g/cm³, apparent porosity of 0.67%, flexural strength of 898.92 MPa, fracture toughness of 6.42 MPa m^1/2, Vickers hardness of 2.81 GPa, and thermal conductivity of 34.69 W m^–1 K^–1, were obtained at 50 vol% solid loading. This work renders low–toxic DMAA gelling system promising prospect in preparation of high–performance Si₃N₄ ceramics by gelcasting.     

Effect of TiO2 addition on the microstructures,mechanical and dielectric properties of porous Si3N4-based ceramics

Porous Si₃N₄-based ceramics with different TiO₂ contents were prepared by gas pressure sintering method. The effects of TiO₂ addition ranging from 0 to 25?wt-% on the phase compositions, microstructures, mechanical performance and dielectric properties were investigated. The addition of TiO₂ significantly promoted the density which increased from 1.64 to about 2.3?g?cm^?3. The mechanical properties of porous Si₃N₄-based ceramics with TiO₂ addition decreased first and then increased with the increase of TiO₂ content, and the flexural strength and elastic modulus are more than 167.4?MPa and 72.8?GPa, respectively, which were higher than that of the Si₃N₄ ceramic without TiO₂ addition. With the increase of TiO₂ content, both the dielectric constant and dielectric loss increased, and the dielectric constant enhanced obviously. These results suggested that the TiO₂ was beneficial for the improvement of mechanical properties and dielectric constant of porous Si₃N₄-based ceramics.     

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.     

Effect of monomer content on physical properties of silicon nitride ceramic green body prepared by gelcasting

The gelcasting technique was employed to prepare Si₃N₄ green body. The monomers used in the research were acrylamide (AM) and N,N′-methylenebisacrylamide (MBAM). The influences of the monomer content (AM and MBAM) and the ratio of monomers (AM/MBAM) on the warpage rate, shrinkage rate, and the flexural strength of Si₃N₄ ceramics green body were investigated. Both warpage rate and shrinkage rate of green body were found to decrease with the increase of monomer content, and monotonically increase with the ratio of monomers after drying. The variation of warpage rate with the ratio of monomers is evident when monomer content is 20 wt.%, but the variations are not evident when monomer contents are 40 and 55 wt.%. The flexural strength of the green body is highest at an optimum value of the monomers ratio, and increases with increasing monomer content, reaching 50–90 MPa when monomer contents are 40 and 55 wt.%.     

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.     

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.     

Low temperature sintering of Si3N4 ceramics by spark plasma sintering technique

Abstract

Abstract

Low temperature sintering of α‐Si₃N₄ matrix ceramics was developed in the present study using 4?wt‐%MgO together with Al₂O₃ or AlPO₄ as the sintering additives and spark plasma sintering technique. The results suggested that α‐Si₃N₄ ceramics could be densified at low sintering temperature by adjusting both the sintering temperature and sintering additive content. For low temperature sintered α‐Si₃N₄ ceramics, using MgO and Al₂O₃ as the sintering additives, the densification is not complete at a temperature lower than 1600°C, and the mechanical strength is <200?MPa. When MgO and AlPO₄ were used as the sintering additives, the increase in AlPO₄ content not only declines the sintering temperature but also promotes the mechanical property of the sintered Si₃N₄ ceramics. It was the AlPO₄ phosphate binder that played a significant role in low temperature sintering of Si₃N₄ ceramics.     

Highly porous ZrO2 ceramics fabricated by a camphene-based freeze-casting route: Microstructure and properties

A camphene-based freeze-casting method was adopted to create ceramics with aligned, equiaxed pores applied so far exclusively for ceramics—is demonstrated for ZrO₂ porous ceramics. The pore volume fraction, channel size and pore shape were controlled by varying the freezing temperature, solid content and sintering condition. After sublimation of camphene, the samples were sintered for 2 h at elevated temperatures ranging from 1400 to 1550 °C. The initial level of solid loading played a primary role in the resulting porosity of the product. The porosity decreased from 82.5 to 65.5 vol.% when the solid loading was increased from 10 to 20 vol.%. The relationship of the compressive strength versus initial solid loading and sintering temperature was discussed. This technique is considered potentially useful in fabricating novel porous ceramics with special structure, and introduces a new application field of freeze-casting.     

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.     

Effect of carboxymethyl cellulose addition on the properties of Si3N4 ceramic foams

The effect of carboxymethyl cellulose (CMC) addition on the preparation of Si₃N₄ ceramic foam by the direct foaming method was investigated. The addition of CMC in the foam slurry can reduce the surface tension, increase the viscoelasticity of foams, and improve their stability and fluidity. The foam ceramics show low shrinkage during drying owing to the CMC and the gelation of acrylamide monomers. The surface structure of dried foam is uniform, and there are no macropores and cracks on the surface. The sintered Si₃N₄ foam ceramics have very uniform pore distribution with average pore size of about 16 μm; the flexure strength is as high as 3.8–77.2 MPa, and the porosity is about 60.6–82.1%.     

Effect of TiO2 addition on thermal and mechanical properties of Y-Si-Al-O-N glasses

Y-Si-Al-O-N glasses are intergranular phases in silicon nitride based ceramics in which the composition and volume fraction of oxynitride glass phases determine the sintering/shrinkage behaviour. Several investigations on oxynitride glass formation and properties have shown that addition of nitrogen increases glass transition and softening temperatures, viscosity, elastic modulus and hardness. In the present study, effect of TiO₂ addition on thermal and mechanical properties of Y-Si-Al-O-N glasses is investigated since the most typical Si₃N₄ ceramics for bearing applications are fabricated using a Si₃N₄-Y₂O₃-Al₂O₃-TiO₂-AlN system. Addition of TiO₂ is effective in preparing Y-Si-Al-O-N glasses with lower glass transition temperatures and with higher hardness.     

Thermal shock resistance of in situ formed Si2N2O–Si3N4 composites by gelcasting

Thermal shock resistance of Si₂N₂O–Si₃N₄ composites was evaluated by water quenching and subsequent three-point bending tests of strength diminution. Si₂N₂O–Si₃N₄ composites which was prepared with in situ liquid pressureless sintering process using Yb₂O₃ and Al₂O₃ powders as sintering additives by gelcasting showed no macroscopic cracks and the critical temperature difference (ΔT_c) could be up to 1400 °C. A mass of pores existed in the sintered body and the irregular shaped fibers extended from the pores increased the thermal shock property.     

导电 Si3N4 基复相陶瓷研究进展

Si_3N_4陶瓷具有优异的力学性能和导热性能,然而其固有的高硬度和脆性极大地限制了其加工性能。通过添加导电相改善Si3N4陶瓷的导电性能可实现对Si_3N_4陶瓷的电火花加工。添加的导电相主要包括钛基化合物(TiN、TiC、TiC N、TiB_2)、锆基化合物(Zr B_2、Zr N)和MoSi_2等导电陶瓷以及碳纳米管(CNT)、碳纳米纤维(CNF)、石墨烯纳米片(GNP)等导电碳基纳米材料。本论文详细回顾了Si_3N_4基导电陶瓷的研究进展,并对今后Si_3N_4基导电陶瓷的发展趋势进行了展望。     

Preparation of Si3N4 porous ceramics via foam-gelcasting and microwave-nitridation method

Si₃N₄ porous ceramics with improved mechanical strength were fabricated for the first time by a combined foam-gelcasting and microwave-nitridation method at 1273–1373?K. The Si₃N₄ porous samples prepared at 1373?K/20?min with the porosity of 68.9% had respectively flexural and compressive strength as high as 8.1 and 20.8?MPa, which values were comparable or even superior to those of Si₃N₄ porous ceramics prepared previously by the conventional heating technique at a much higher temperature of 1773–1973?K, indicating that present preparation strategy is feasible to prepare high quality Si₃N₄ porous ceramic at a much milder condition. Moreover, the thermal conductivity of as-prepared Si₃N₄ porous ceramics at 1073?K was as low as 1.697?W/(m?K), suggesting it could be a potentially good heat insulating material for aluminum electrolyte cells.     

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.     

Effects of solid loading and calcination temperature on microstructure and properties of porous Si3N4 ceramics by aqueous gelcasting using DMAA system

Herein, a low–toxic N, N–dimethylacrylamide (DMAA) system was used in preparation of porous Si₃N₄ ceramics by aqueous gelcasting, and variations in microstructure and properties with solid loading and calcination temperature were systematically investigated. In the considered solid loading range of 28–44 vol%, all the slurries exhibited superior rheological properties (≤145 mPa⋅s at 95.40 s⁻¹ for 44 vol% solid loading) perfectly suitable for casting. With increasing solid loading, a decreased bulk density (1.71–1.69 g/cm³), volume shrinkage (37.73–13.77%) and flexural strength (46.56–26.75 MPa) of green bodies were obtained, exhibiting better mechanical properties than those derived from the conventional acrylamide (AM) system. Regarding Si₃N₄ ceramics with various solid loadings, the increase in calcination temperature favored the phase transformation α→β–Si₃N₄ and β–Si₃N₄ growth, however, the increased solid loading exhibited an inhibiting effect on those since mass transport in gas phase was blocked due to the disruption of pore connectivity. The resulting microstructure changes imparted Si₃N₄ ceramics increasing flexural strength (110.36–367.88 MPa), fracture toughness (2.54–5.03 MPa⋅m^1/2), as well as decreasing porosity (54.21–41.05%) and pore size (0.38–0.33 μm). This work demonstrates the potential research value of DMAA system in preparing high–performance porous Si₃N₄ ceramics through gelcasting technique.     

Effects of AlN inorganic binder on the properties of porous Si3N4 ceramics prepared by selective laser sintering

Porous Si₃N₄ ceramics are widely used in the aerospace field due to its lightweight, high-strength, and high wave transmission. Traditional manufacturing methods are difficult to fabricate complex structural and functional ceramic parts. In this paper, selective laser sintering (SLS) technology was applied to prepare porous Si₃N₄ ceramics using AlN as an inorganic binder. And the effects of AlN content on the properties of the obtained ceramic samples were explored. As the AlN content increased, nano-Al₂O₃ and nano-SiO₂ formed the eutectic liquid phase, enhancing the sintering densification and phase transformation of Si₃N₄ poly-hollow microspheres (PHMs). The island-like partial densification structures in Si₃N₄ green bodies increased. During the high-temperature sintering, the eutectic liquid phase partially transformed into the mullite phase or reacted with AlN and Si₃N₄ to form the Sialon phase. With the increase of AlN content, the fracture mode of Si₃N₄ ceramics changed from fracturing along PHMs to fracturing across PHMs. The bonding depth between PHMs increased and the connection between the grains was tighter, so the Si₃N₄ ceramics became denser. With the increase of AlN addition, the total porosity of the porous Si₃N₄ ceramics tended to decrease and the flexural strength gradually increased. When AlN content was 20 wt%, the total porosity and the flexural strength were 33.6% and 23.9 MPa, respectively. The addition of AlN inorganic binder was carried out to develop a novel way to prepare high-performance porous Si₃N₄ ceramics by SLS.     

Microwave dielectric properties of SnO2-doped CaSiO3 ceramics

SnO₂-doped CaSiO₃ ceramics were successfully synthesized by a solid-state method. Effects of different SnO₂ additions on the sintering behavior, microstructure and dielectric properties of Ca(Sn_1−xSi_x)O₃ (x=0.5–1.0) ceramics have been investigated. SnO₂ improved the densification process and expanded the sintering temperature range effectively. Moreover, Sn⁴⁺ substituting for Si⁴⁺ sites leads to the emergence of Ca₃SnSi₂O₉ phase, which has a positive effect on the dielectric properties of CaO–SiO₂–SnO₂ materials, especially the Qf value. The Ca(Sn_0.1Si_0.9)O₃ ceramics sintered at 1375 °C possessed good microwave dielectric properties: ε_r =7.92, Qf =58,000 GHz and τ_f=−42 ppm/°C. The Ca(Sn_0.4Si_0.6)O₃ ceramics sintered at 1450 °C also exhibited good microwave dielectric properties of ε_r=9.27, Qf=63,000 GHz, and τ_f=−52 ppm/°C. Thus, they are promising candidate materials for millimeter-wave devices.