Polymer-derived SiHfN ceramics: From amorphous bulk ceramics with excellent mechanical properties to high temperature resistant ceramic nanocomposites

Within the present work, additive-free amorphous bulk SiHfN ceramics with excellent mechanical properties were prepared by a resource-efficient low-temperature molding method, namely warm-pressing. As densification mechanism viscous flow has been identified based on cross-linking reaction. The critical problems concerning gas evolution and crystallization inducing bloating and cracking are addressed through controlled thermolysis and pressure. The microstructural evolution of the SiHfN ceramics indicates that the incorporation of Hf in perhydropolysilazane not only increases the ceramic yield (97.4 wt%) and crystallization resistance (1300 °C), but also suppresses the transformation from α-Si₃N₄ to β-Si₃N₄ at high temperatures (1700 °C). Especially, HfN/α-Si₃N₄ nanocomposites converted by the SiHfN ceramics at 1500 °C show a slight weight loss of 3.13 wt%, indicating the high temperature resistance of the ceramic nanocomposites. The method proposed in this work opens a new strategy to fabricate additive-free polycrystalline Si₃N₄- and amorphous Si₃N₄-based (nano)composites.     

Dielectric properties of Si3N4–SiCN composite ceramics in X-band

Si₃N₄–SiCN composite ceramics were successfully fabricated through precursor infiltration pyrolysis (PIP) method using polysilazane as precursor and porous Si₃N₄ as preform. After annealed at temperatures varying from 900 °C to 1400 °C, the phase composition of SiCN ceramics, electrical conductivity and dielectric properties of Si₃N₄–SiCN composite ceramics over the frequency range of 8.2–12.4 GHz (X-band) were investigated. With the increase of annealing temperature, the content of amorphous SiCN decreases and that of N-doped SiC nano-crystals increases, which leads to the increase of electrical conductivity. After annealed at 1400 °C, the average real and imaginary permittivities of Si₃N₄–SiCN composite ceramics are increased from 3.7 and 4.68 × 10^?3 to 8.9 and 1.8, respectively. The permittivities of Si₃N₄–SiCN composite ceramics show a typical ternary polarization relaxation, which are ascribed to the electric dipole and grain boundary relaxation of N-doped SiC nano-crystals, and dielectric polarization relaxation of the in situ formed graphite. The Si₃N₄–SiCN composite ceramics exhibit a promising prospect as microwave absorbing materials.     

From design to characterization of zirconium nitride/silicon nitride nanocomposites

ZrN/Si₃N₄ nanocomposites have been prepared by chemically crosslinking two polysilazanes with a zirconium-based compound and subsequent heat-treatment at temperatures ranging from 1000 to 1600 °C. The polymer synthesis has been systematically investigated using FT-IR, solid-state NMR, and elemental analyses. Then, the pyrolysis under ammonia at 1000 °C trigering the thermo-chemical polymer-to-ceramic conversion was examined, leading to X-ray amorphous ceramics with yields governed by the chemistry of the neat polysilazane. Investigations of the structural evolution of the single-phase amorphous ceramic network above 1000 °C by X-ray diffraction and Raman spectroscopy pointed out that the ZrN phase already segregated at 1400 °C and formed highly crystalline ZrN/Si₃N₄ nanocomposites at 1600 °C. HRTEM investigations validated the unique nanostructural feature of the nanocomposites made of ZrN nanocrystals distributed in α- and β-Si₃N₄ phases. Our preliminary investigations of the optical properties showed that these structural changes allowed tuning the optical properties of ZrN/Si₃N₄ nanocomposites.     

Effects of oxygen on the thermal stability of silicon nitride fibers

Two types of Si₃N₄ fibers with different oxygen contents were annealed in a nitrogen atmosphere at 1500 °C for 1 h. After annealing, the fiber (SN-L) containing 0.5 wt% oxygen crystallized to α-Si₃N₄ but lost its strength, whereas the fiber (SN-H) containing 4.2 wt% oxygen was amorphous and retained 63.6% of its strength. The phase transition in these fibers was mainly influenced by the oxygen level. The lower oxygen content in the SN-L favored the precipitation of an almost stoichiometric composition of α-Si₃N₄ initially at ~1450 °C with an activation energy (Ea) of 663.357 kJ/mol. Nanopores existing naturally in the fiber promoted crystallization via heterogeneous nucleation. SN-H precipitated as an amorphous SiN_xO_y metaphase preferentially at ~1400 °C with an Ea of 440.434 kJ/mol, owing to the higher oxygen content approaching that of Si₂N₂O. SiN_xO_y inhibited the crystallization of α-Si₃N₄, making SN-H more thermally stable than SN-L at temperatures above 1500 °C.     

Non-additive sintering of Si2N2O ceramic with enhanced high-temperature strength,oxidation resistance,and dielectric properties

The high-temperature mechanical and dielectric properties of Si₂N₂O ceramics are often limited by the introduction of a sintering aid. Herein, dense Si₂N₂O was prepared at 1700 °C by hot-pressing oxidized amorphous Si₃N₄ powder without sintering additives. A homogeneous network with short-range order and a SiN₃O structure was formed in the oxidized amorphous Si₃N₄ powder during the hot-pressing process. Si₂N₂O crystals preferentially nucleated at positions within the SiN₃O structure and grew into rod-like and plate-like grains. Fully dense ceramics with mainly crystalline Si₂N₂O and some residual amorphous phases were obtained. The as-prepared Si₂N₂O possessed a good flexural strength of 311 ± 14.9 MPa at 1400 °C, oxidation resistance at 1500 °C, and a low dielectric loss tangent of less than 5 × 10⁻³ at 1000 °C.     

Fabrication of high thermal conductivity silicon nitride ceramics by pressureless sintering with MgO and Y2O3 as sintering additives

The fabrication of silicon nitride (Si₃N₄) ceramics with a high thermal conductivity was investigated by pressureless sintering at 1800 °C for 4 h in a nitrogen atmosphere with MgO and Y₂O₃ as sintering additives. The phase compositions, relative densities, microstructures, and thermal conductivities of the obtained Si₃N₄ ceramics were investigated systemically. It was found that at the optimal MgO/Y₂O₃ ratio of 3/6, the relative density and thermal conductivity of the obtained Si₃N₄ ceramic doped with 9 wt% sintering aids reached 98.2% and 71.51 W/(m·K), respectively. EDS element mapping showed the distributions of yttrium, magnesium and oxygen elements. The Si₃N₄ ceramics containing rod-like grains and grain boundaries were fabricated by focused ion beam technique. TEM observations revealed that magnesium existed as an amorphous phase and that yttrium produced a new secondary phase.     

Polymer-derived Co2Si(Co)/SiCN composite ceramics with tunable microwave absorption properties

In this paper, Co₂Si(Co)/SiCN composite ceramics were synthesized by simple precursor-derived ceramics method. The phase composition, morphology, and microwave absorption properties of Co₂Si(Co)/SiCN composite ceramics at different pyrolysis temperatures (1000–1400°C) were studied. When pyrolysis temperature was 1300°C, carbon nanowires (CNWs), Co₂Si, Si₂N₂O, SiC and Si₃N₄ were in situ generated and the best electromagnetic wave (EMW) absorption performance was obtained. The minimum reflection loss reached−50.04 dB at 4.81 mm, and the effective absorption bandwidth broadened to 3.48 GHz (14.52–18 GHz) at 1.31 mm. The excellent EMW absorption performance mainly comes from the coexistence of multiple loss mechanisms, including the magnetic loss of Co₂Si, the conduction loss of CNWs, and the heterogeneous interfaces polarization between varieties of nanocrystals and amorphous ceramic matrix. By adjusting the sample thickness from 1 to 5 mm, the effective absorption of S1300 can cover the entire X and Ku bands, from 3.36 to 18 GHz. This study provides a simple way to synthesize high performance ceramic-based microwave absorbing materials.     

Preceramic Polymer‐Derived SiAlON as Sintering Aid for Silicon Nitride

Two kinds of sintering additives based on the polysiloxanes or polysilazanes filled with nano‐sized powders as SiAlON precursors were tested for the densification of Si₃N₄‐based ceramics. The results showed that both systems can be successfully used as additives for the preparation of Si₃N₄ ceramics with favorable mechanical characteristics. The ceramics were sintered with 18 wt% of preceramic polymer‐based mixture, and good fracture resistance and high hardness values were obtained after sintering in optimized conditions (temperature, dwell time, nitrogen pressure). Higher densification temperatures and longer holding times were required for sintering of samples with polysilazane‐based precursors. The best toughness values were approximately 5 MPa·m^0.5, while the highest hardness was about 19 GPa. The differences in mechanical properties of the prepared composites can be related to the phase composition, microstructure and different chemical bonds present in the ceramic residue generated upon pyrolysis and final densification.     

Preparation and characterization of Si3N4-based composite ceramic tool materials by microwave sintering

Si₃N₄-based composite ceramic tool materials with (W,Ti)C as particle reinforced phase were fabricated by microwave sintering. The effects of the fraction of (W,Ti)C and sintering temperature on the mechanical properties, phase transformation and microstructure of Si₃N₄-based ceramics were investigated. The frictional characteristics of the microwave sintered Si₃N₄-based ceramics were also studied. The results showed that the (W,Ti)C would hinder the densification and phase transformation of Si₃N₄ ceramics, while it enhanced the aspect-ratio of β-Si₃N₄ which promoted the mechanical properties. The Si₃N₄-based composite ceramics reinforced by 15 wt% (W,Ti)C sintered at 1600 °C for 10 min by microwave sintering exhibited the optimum mechanical properties. Its relative density, Vickers hardness and fracture toughness were 95.73 ± 0.21%, 15.92 ± 0.09 GPa and 7.01 ± 0.14 MPa m^1/2, respectively. Compared to the monolithic Si₃N₄ ceramics by microwave sintering, the sintering temperature decreased 100 °C,the Vickers hardness and fracture toughness were enhanced by 6.7% and 8.9%, respectively. The friction coefficient and wear rate of the Si₃N₄/(W,Ti)C sliding against the bearing steel increased initially and then decreased with the increase of the mass fraction of (W,Ti)C., and the friction coefficient and wear rate reached the minimum value while the fraction of (W,Ti)C was 15 wt%.     

A comprehensive study on the influence of the polyorganosilazane chemistry and material shape on the high temperature behavior of titanium nitride/silicon nitride nanocomposites

The high temperature crystallization behavior of polytitanosilazane-derived amorphous SiTiN ceramics was investigated in a nitrogen atmosphere using XRD, Raman spectroscopy, TEM, SEM and BET. At 1400 °C, TiN is the first phase to nucleate in SiTiN ceramics forming nanocomposites with a homogeneous distribution of TiN nanocrystals within an amorphous Si₃N₄ matrix. Above 1400 °C, XRD indicates that the temperature at which Si₃N₄ crystallizes depends on the volume fraction of TiN present in nanocomposites. This is closely related to the chemistry of the polyorganosilazanes used to synthesize polytitanosilazanes. The use of perhydridopolysilazane, the most reactive polyorganosilazane, allows preparing TiN/Si₃N₄ nanocomposites with a remarkable stability of the amorphous matrix up to 1800 °C as mesoporous materials and powders. Dense monoliths crystallize earlier than the powder analogs because of the use of an ammonia pre-treatment before polymer warm-pressing.     

High-temperature properties and interface evolution of C/SiBCN composites prepared by precursor infiltration and pyrolysis

C/SiBCN composites with a density of 1.64 g/cm³ were prepared via precursor infiltration and pyrolysis and the bending strength and modulus at room temperature was 305 MPa and 53.5 GPa. The precursor derived SiBCN ceramics showed good thermal stability at 1600 °C and the SiC and Si₃N₄ crystals appeared above 1700 °C. The bending strength of the composites was 180 MPa after heat treatment at 1500 °C, and maintained at 40 MPa-50 MPa after heat treatment for 2 h at 1600 °C–1900 °C. In C/SiBCN composites, SiBCN matrix could retain amorphous up to 1500 °C and SiC grains appeared at 1600 °C but without Si₃N₄. The reason for no detection of Si₃N₄ was that the carbon fiber reacted with Si₃N₄ to form an interface layer (composed of SiC and unreacted C) and a polycrystalline transition layer (composed of B and C elements), leading to the degradation of the mechanical properties.     

Silicon Oxynitride Ceramics Prepared by Plasma Activated Sintering of Nanosized Amorphous Silicon Nitride Powder without Additives

Si₂N₂O ceramics were prepared by plasma activated sintering using nanosized amorphous Si₃N₄ powder without sintering additives within a temperature range of 1400°C–1600°C in vacuum. A mixed Si–N_4?n–O_n (n = 0, 1…4) amorphous structure was formed in the process of sintering, and Si₂N₂O crystals were nucleated where the local structure was similar with Si₂N₂O. After sintering at 1600°C, the Si₂N₂O ceramic was composed of elongated plate‐like Si₂N₂O grains and amorphous phase. The Si₂N₂O grains showed a width of less than 100 nm and a very high aspect ratio.     

In situ synthesis of Si2N2O/Si3N4 composite ceramics using polysilyloxycarbodiimide precursors

In situ synthesis of Si₂N₂O/Si₃N₄ composite ceramics was conducted via thermolysis of novel polysilyloxycarbodiimide ([SiOSi(NCN)₃]_n) precursors between 1000 and 1500 °C in nitrogen atmosphere. The relative structures of Si₂N₂O/Si₃N₄ composite ceramics were explained by the structural evolution observed by electron energy-loss spectroscopy but also by Fourier transform infrared and ²⁹Si-NMR spectrometry. An amorphous single-phase Si₂N₂O ceramic with porous structure with pore size of 10–20 μm in diameter was obtained via a pyrolyzed process at 1000 °C. After heat-treatment at 1400 °C, a composite ceramic was obtained composed of 53.2 wt.% Si₂N₂O and 46.8 wt.% Si₃N₄ phases. The amount of Si₂N₂O phase in the composite ceramic decreased further after heat-treatment at 1500 °C and a crystalline product containing 12.8 wt.% Si₂N₂O and 87.2 wt.% Si₃N₄ phases was obtained. In addition, it is interesting that residual carbon in the ceramic composite nearly disappeared and no SiC phase was observed in the final Si₂N₂O/Si₃N₄ composite.     

Low‐Temperature Preparation of β‐Si3N4 Porous Ceramics with a Small Amount of Li2O–Y2O3

Porous β‐Si₃N₄ ceramics are sintered at 1600°C in N₂ and postheat treated at 1500°C under vacuum using Li₂O and Y₂O₃ as the sintering additives. The partial sintering and phase transformation are promoted at low temperature by the addition of Li₂O. The addition of Y₂O₃ is advantageous for the formation of high aspect ratio β‐Si₃N₄ grains. After postheat treatment, a large amount of intergranular glassy phase is removed, and the Li content in the samples is decreased. By this method, the β‐Si₃N₄ porous ceramic with a porosity of 54.1% and high flexural strength of 110 ± 8.1 MPa can be prepared with a small amount of sintering additives, 0.66 wt% Li₂O and 0.33 wt% Y₂O₃, and it is suitable for high‐temperature applications.     

Structure–property relations of ferroelectric BaTiO3 ceramics containing nano-sized Si3N4 particulates

Barium titanate/silicon nitride (BaTiO₃/xSi₃N₄) powder (when x = 0, 0.1, 0.5, 1 and 3 wt%) were prepared by solid-state mixed-oxide method and sintered at 1400 °C for 2 h. X-ray diffraction result suggested that tetragonality (c/a) of the BaTiO₃/xSi₃N₄ ceramics increased with increasing content of Si₃N₄. Density and grain size of BaTiO₃/xSi₃N₄ ceramic were found to increase for small addition (i.e. 0.1 and 0.5 wt%) of Si₃N₄ mainly due to the presence of liquid phase during sintering. BaTiO₃ ceramics containing such amount of Si₃N₄ also showed improved dielectric and ferroelectric properties.     

Enhanced bending strength and microwave dielectric properties of Li2MgTi3O8 ceramics by adding Si3N4 reinforcing phase

In the 5G era, the dielectric materials used in microwave electronic components must have not only have good microwave dielectric characteristics but also excellent structural characteristics. Li₂MgTi₃O₈ (LMT) ceramics have excellent microwave dielectric properties; however, their low bending strength limits their further applications in the 5G era. In this work, the dielectric properties and bending strength of LMT ceramics were optimized by the addition of Si₃N₄ reinforcing phase using a solid-phase method, and the effects of Si₃N₄ addition on the sintering properties, microscopic structure, crystalline phase, dielectric properties and bending strength of ceramics were investigated. The X-ray diffraction pattern indicates that all ceramics exhibit spinel structure. Combined with the phenomenon of grain reduction in the SEM graph, it indicates that the addition of Si₃N₄ can inhibit the grain growth and achieve the purpose of fine-grain strengthening. The dispersion enhancement of second phase particles is also one of the reasons for the increase of bending strength. LMT ceramics doped with 0.5 wt% Si₃N₄ exhibited the maximum bending strength after sintering at 1050 °C for 4 h, which was 76.97% higher than that of pure LMT ceramics. In addition, the ceramics exhibited outstanding dielectric properties: a dielectric constant of 23.20, quality factor of 49344 GHz, and temperature coefficient of ?5.90 ppm/°C. The high bending strength and good microwave dielectric properties indicate that Si₃N₄-added LMT ceramics can be effectively applied in the 5G era.     

A novel method of strong and tough Si3N4 ceramic from the particle-stabilized foam

The brittleness of Si₃N₄ ceramics has always limited its wide application. In this paper, Si₃N₄ ceramics were prepared based on foam. Combining the unique honeycomb structure of the ceramic foams and the self-toughening mechanism of Si₃N₄, the strengthening and toughening of Si₃N₄ ceramics can be further achieved by adjusting the microstructure of Si₃N₄ ceramic foams. The powder particles are self-assembled by particle-stabilized foaming to form a foam body with a honeycomb structure. It was pretreated at different temperatures (1450–1750°C). The microstructure evolution of foamed ceramics at different pretreatment temperatures and the conversion rate of α-Si₃N₄ to β-Si₃N₄ at different pretreatment temperatures were explored. Then the foamed ceramics with different microstructures are hot-press sintered to prepare Si₃N₄ dense ceramics. The effects of different microstructures of foamed ceramics on the strength and toughness of Si₃N₄ ceramics were analyzed. The experimental results show that the relative density of Si₃N₄ ceramics prepared at a particle pretreatment temperature of 1500°C is 97.8%, and its flexural strength and fracture toughness are relatively the highest, which are 1089 ± 60 MPa and 12.9 ± 1.3 MPa m^1/2, respectively. Compared with the traditional powder hot-pressing sintering, the improvement is 21% and 33%, respectively. It is shown that this method of preparing Si₃N₄ ceramics based on foam has the potential to strengthen and toughen Si₃N₄ ceramics.     

Amorphous Si(Al)OC ceramic from polysiloxanes: bulk ceramic processing,crystallization behavior and applications

Here we report on bulk Si–Al–O–C ceramics produced by pyrolysis of commercial poly(methylsilsesquioxane) precursors. Prior to the pyrolysis the precursors were cross-linked with a catalyst, or modified by the sol-gel-technique with an Al-containing alkoxide compound, namely alumatrane. This particular procedure yields amorphous ceramics with various compositions (Si_1.00O_1.60C_0.80, Si_1.00Al_0.04O_1.70C_0.48, Si_1.00Al_0.07O_1.80C_0.49, and Si_1.00Al_0.11O_1.90C_0.49) after thermal decomposition at 1100 °C in Ar depending on the amount of Al-alkoxide used in the polymer reaction synthesis. The as-produced ceramics are amorphous and remain so up to 1300 °C. Phase separation accompanied by densification (1300–1500 °C) and formation of mullite at T > 1600 °C are the stages during heat-treatment. Bulk SiAlOC ceramics are characterized in terms of microstructure and crystallization in the temperature regime ranging from 1100 to 1700 °C. Aluminum-free SiOC forms SiC along with cracking of the bulk compacts. In contrast, the presence of Al in the SiOC matrix forms SiC and mullite and prevents micro cracking at elevated temperatures due to transient viscous sintering. The nano-crystals formed are embedded in an amorphous Si(Al)OC matrix in both cases. Potential application of polysiloxane derived SiOC ceramic in the field of ceramic micro electro mechanical systems (MEMS) is reported.     

The preparation of silicon nitride ceramics by gelcasting and pressureless sintering

A new gelling system based on the polymerization of hydantion epoxy resin and 3,3′-Diaminodipropylamine (DPTA) was successfully developed for fabricating silicon nitride (Si₃N₄) ceramics. The effects of pH value, the dispersant content, solid volume fraction and hydantion epoxy resin amount on the rheological properties of the Si₃N₄ slurries were investigated. The relative density of green body obtained from the solid loading of 52 vol% Si₃N₄ slurry reached up to 62.7%. As the concentration of hydantion epoxy resin increased from 5 wt% to 20 wt%, the flexural strength of Si₃N₄ green body enhanced from 5.3 MPa to 31.6 MPa. After pressureless sintering at 1780 °C for 80 min, the sintered samples exhibited the unique interlocking microstructure of elongated β-Si₃N₄ grains, which was beneficial to improve the mechanical properties of Si₃N₄ ceramics. The relative density, flexural strength and fracture toughness of Si₃N₄ ceramics reached 97.8%, 687 MPa and 6.5 MPa m^1/2, respectively.     

Si3N4-ZrB2 ceramics prepared at low temperature with improved mechanical properties

Si₃N₄-ZrB₂ ceramics were hot-pressed at 1500 °C using self-synthesized fine ZrB₂ powders containing 2.0 wt% B₂O₃ together with MgO-Re₂O₃ (Re = Y, Yb) additives. Both Si₃N₄ and ZrB₂ grains in the hot-pressed ceramics were featured with elongated and equiaxed morphology. The presence of elongated Si₃N₄ and ZrB₂ grains led to the partial texture of the ceramics under the applied pressure. Vickers hardness and fracture toughness of Si₃N₄-ZrB₂ ceramics with MgO-Re₂O₃ additives prepared at low temperature were about 19–20 GPa and 9–11 MPa m^1/2, respectively, higher than the reported values of Si₃N₄-based ceramics prepared at high temperature (1800 °C or above) under the same test method.