Effect of in-situ formed Y2O3 by metal hydride reduction reaction on thermal conductivity of β-Si3N4 ceramics

The effect of YH₂ on densification, microstructure, and thermal conductivity of Si₃N₄ ceramics were investigated by adjusting the amount of YH₂ in the range of 0–4 wt% using a two-step sintering method. Native SiO₂ was eliminated, and Y₂O₃ was in situ formed by a metal hydride reduction reaction, resulting in various Y₂O₃/SiO₂ ratios. Full densification of YH₂-doped samples could be achieved after sintering at 1900 °C for 4 h. The Y₂O₃/SiO₂ ratio had a significant influence on the composition of crystalline secondary phases. Besides, the increased Y₂O₃/SiO₂ ratio is conducive not only to the grain growth but also to the reduction of activity of SiO₂ in the liquid phase, resulting in enlarged purified grains, reduced volume fraction of intergranular phases and increased Si₃N₄-Si₃N₄ contiguity. Ultimately, the thermal conductivity increased by 29 % from 95.3 to 123.0 W m⁻¹ K⁻¹ after sintering at 1900 ℃ for 12 h by the substitution of Y₂O₃ with YH₂.     

Effect of lattice impurities on the thermal conductivity of β-Si3N4

Effect of impurities in the crystal lattice and microstructure on the thermal conductivity of sintered Si₃N₄ was investigated by the use of high-purity β-Si₃N₄ powder. The sintered materials were fabricated by gas pressure sintering at 1900 °C for 8 and 48 h with addition of 8 wt.% Y₂O₃ and 1 wt.% HFO₂. A chemical analysis was performed on the loose Si₃N₄ grains taken from sintered materials after the chemical treatment. Aluminum was not removed from Si₃N₄ grains, which originated from the raw powder of Si₃N₄. The coarse grains had fewer impurities than the fine grains. Oxygen was the major impurity in the grains, and gradually decreased during grain growth. The thermal conductivity increased from 88 Wm⁻¹ K⁻¹ (8 h) to 120 Wm⁻¹ K⁻¹ (48 h) as the impurities in the crystal lattice decreased. Purification by grain growth thus improved the thermal conductivity, but changing grain boundary phases might also influence the thermal conductivity.     

Influence of α-Si3N4 coarse powder on densification,microstructure, mechanical properties,and thermal behavior of silicon nitride ceramics

Silicon nitride (Si₃N₄) ceramics, with different ratios of fine and coarse α-Si₃N₄ powders, were prepared by spark plasma sintering (SPS) and heat treatment. Further, the influence of coarse α-Si₃N₄ powder on densification, microstructure, mechanical properties, and thermal behavior of Si₃N₄ ceramics was systematically investigated. Compared with fine particles, coarse particles exhibit a slower phase transition rate and remain intact until the end of SPS. The remaining large-sized grains of coarse α-Si₃N₄ induce extensive growth of neighboring β-Si₃N₄ grains and promote the development of large elongated grains. Noteworthy, an appropriate number of large elongated grains distributed among fine-grained matrix forms bimodal microstructural distribution, which is conducive to superior flexural strength. Herein, Si₃N₄ ceramics with flexural strength of 861.34 MPa and thermal conductivity of 65.76 W m⁻¹ K⁻¹ were obtained after the addition of 40 wt% coarse α-Si₃N₄ powder.     

Simultaneous improvement in porosity and strength of porous β-Si3N4 ceramics by formation of ultrafine fibrous grains

Si₃N₄ ceramic with ultrafine fibrous grains are expected to exhibit remarkable mechanical properties. In this work, highly porous Si₃N₄ ceramic monoliths composed of ultrafine fibrous grains were developed via a novel vapor-solid carbothermal reduction nitridation (V-S CRN) reaction between SiO vapor and green bodies comprised of carbon nanotubes (CNTs), α-Si₃N₄ diluents and Y₂O₃ in a N₂ atmosphere. The unique fibrous grains-interconnected structure was developed through in-situ formation of Si₃N₄ and following liquid phase sintering. The porous Si₃N₄ monoliths with porosity of 61–78% was developed by controlling the contents of α-Si₃N₄ diluents and densities of the CNT green bodies. With increasing of the α-Si₃N₄ contents, Si₃N₄ fibrous grains with an aspect ratio of approximate or higher than 20 could be achieved, and the grains were gradually refined. For the samples with 40 wt% α-Si₃N₄, the minimum mean grain diameter and pore size of 164 nm and 0.79 μm were achieved, respectively, and the resultant porous Si₃N₄ monolith exhibited a flexural strength of as high as 73–102 MPa with the porosity of 61–73%, which is much higher than that of the reported in literature. The improvement of mechanical strength could be attributed to the densely interconnected bird's nests structure formed by the ultrafine fibrous grains. The effects of the α-Si₃N₄ diluents on the resulting porous Si₃N₄ monolith via this method were analyzed.     

Improved thermal conductivity of β-Si3N4 ceramics by lowering SiO2/Y2O3 ratio using YH2 as sintering additive

A two-step sintering process was conducted to produce β-Si₃N₄ ceramics with high thermal conductivity. During the first step, native SiO₂ was eliminated, and Y₂O₃ was in situ generated by a metal hydride reduction process, resulting in a high Y₂O₃/SiO₂ ratio. The substitution YH₂ for Y₂O₃ endow Si₃N₄ ceramics with an increase of 29% in thermal conductivity from 95.3 to 123 W m⁻¹ K⁻¹ after sintered at 1900°C for 12 hours despite an inferior sinterability. This was primarily attributed to the purified enlarged grains, devitrified grain boundary phase, and reduced lattice oxygen content in the YH₂-MgO-doped material.     

Effect of the addition of β-Si3N4 nuclei on the thermal conductivity of β-Si3N4 ceramics

Various microstructures of β-Si₃N₄ were fabricated, with or without the addition of β-Si₃N₄ seed particles to high-purity β-Si₃N₄ powder, using Yb₂O₃ and ZrO₂ as sintering additives, by gas-pressure sintering at 1950 °C for 16 h. The thermal conductivity of the specimen without seeds was 140 W·(m·K)⁻¹, and the specimen exhibited a bimodal microstructure with abnormally grown grains. The thermal conductivity of the specimen with 24 vol.% seed addition was 143 W·(m·K)⁻¹, and this specimen had the bimodal microstructure with finer grain size than that without the seeded material, but maintained the same amount of large grains (⩾2 μm in diameter) as in the specimen without the seeds. This finding indicates that the thermal conductivity of β-Si₃N₄ is controlled by the amount of reprecipitated large grains, rather than by the grain size of the β-Si₃N₄.     

A facile method to produce rodlike β-Si3N4 seed crystallites for bimodal structure controlling

β-Si₃N₄ rodlike seed crystallites were successfully produced by single-step heat treatment of commercial α-Si₃N₄ powder at 1900°C for 20 h under an N₂ gas pressure of 980 kPa. The average diameter, length, and aspect ratio of the seed crystallites were 0.73 μm, 1.37 μm, and 1.86, respectively. The α- ⇀ β-Si₃N₄ phase transformation proceeded mainly at 1900°C, and this temperature was lower than the theoretical α-Si₃N₄ dissociation temperature (1933°C) under N₂ gas pressure of 980 kPa. The formation of metastable solid solution due to the dissolution of O impurity into the α-Si₃N₄ crystal lattice was suggested as the driving force for the present oxide additive-free α- ⇀ β-Si₃N₄ phase transformation. β-Si₃N₄ ceramics were fabricated by liquid phase sintering promoted by an additive system of 1 wt% MgO with 3 wt% Gd₂O₃. Starting α-Si₃N₄ powder with 10 vol% rodlike β-Si₃N₄ seed crystallites prepared in this study and an extended sintering time for up to 20 h at 1950°C resulted in the formation of bimodal microstructure composed of fine matrix grains and large elongated grains originated from the seed crystallites. The β-Si₃N₄ ceramics exhibited improved fracture toughness and thermal conductivity of 5.9 ± 0.8 MPa m^−1/2 and 109.3 ± 0.4 W m⁻¹ K⁻¹, respectively, retaining a high fracture strength of about 1 GPa.     

Microstructure and mechanical properties of α/β-Si3N4 composite ceramics with novel ternary additives prepared via spark plasma sintering

In this study, α/β-Si₃N₄ composite ceramics with high hardness and toughness were fabricated by adopting two different novel ternary additives, ZrN–AlN–Al₂O₃/Y₂O₃, and spark plasma sintering at 1550 °C under 40 MPa. The phase composition, microstructure, grain distribution, crack propagation process and mechanical properties of sintered bulk were investigated. Results demonstrated that the sintered α/β-Si₃N₄ composite ceramics with ZrN–AlN–Al₂O₃ contained the most α phase, which resulted in a maximum Vickers hardness of 18.41 ± 0.31 GPa. In the α/β-Si₃N₄ composite ceramics with ZrN–AlN–Y₂O₃ additives, Zr₃AlN MAX-phase and ZrO phase were found and their formation mechanisms were explained. The fracture appearance presented coarser elongated β-Si₃N₄ grains and denser microstructure when 20 wt% TiC particles were mixed into Si₃N₄ matrix, meanwhile, exhibited maximum mean grain diameter of 0.98 ± 0.24 μm. As a result, the compact α/β-Si₃N₄ composite ceramics containing ZrN–AlN–Y₂O₃ additives and TiC particles displayed the optimal bending strength and fracture toughness of 822.63 ± 28.75 MPa and 8.53 ± 0.21 MPa?m^1/2, respectively. Moreover, the synergistic toughening of rod-like β-Si₃N₄ grains and TiC reinforced particles revealed the beneficial effect on the enhanced fracture toughness of Si₃N₄ ceramic matrix.     

Effect of seeding on the thermal conductivity of self-reinforced silicon nitride

Thermal conductivity of Si₃N₄ containing large β-Si₃N₄ particles as seeds for grain growth was investigated. Seeds addition promotes growth of β-Si₃N₄ grains during sintering to develop the duplex microstructure. The thermal conductivity of the material sintered at 1900 °C improved up to 106 W m⁻¹ K⁻¹, although that of unseeded material was 77 Wm⁻¹ K⁻¹. Seeds addition leads to reduction of the sintering temperature with developing the duplex microstructure and with improving the thermal conductivity, which benefits in terms of production cost of Si₃N₄ ceramics with thermal conductivity. ©     

Enhanced thermal conductivity in Si3N4 ceramic with the addition of Y2Si4N6C

Si₃N₄ ceramic was densified at 1900°C for 12 hours under 1 MPa nitrogen pressure, using MgO and self‐synthesized Y₂Si₄N₆C as sintering aids. The microstructures and thermal conductivity of as‐sintered bulk were systematically investigated, in comparison to the counterpart doped with Y₂O₃‐MgO additives. Y₂Si₄N₆C addition induced a higher nitrogen/oxygen atomic ratio in the secondary phase by introducing nitrogen and promoting the elimination of SiO₂, resulting in enlarged grains, reduced lattice oxygen content, increased Si₃N₄‐Si₃N₄ contiguity and more crystallized intergranular phase in the densified Si₃N₄ specimen. Consequently, the substitution of Y₂O₃ by Y₂Si₄N₆C led to a great increase in ~30.4% in thermal conductivity from 92 to 120 W m^?1 K^?1 for Si₃N₄ ceramic.     

Mechanical properties and microstructure of Al2O3-SiCw ceramic tool material toughened by Si3N4 particles

Al₂O₃-SiC_w toughened ceramic tools play vital role in high-speed machining of nickel-based superalloys due to their superior mechanical properties. Herein, owing to synergistic toughening mechanism, α-Si₃N₄ particles are employed as reinforcement phase into Al₂O₃-SiC_w ceramic composite to optimize mechanical properties of Al₂O₃-SiC_w ceramic tools. Moreover, the influence of Si₃N₄ content and sintering parameters on microstructure and mechanical properties of Al₂O₃-20 vol%SiC_w ceramic tool material is systematically investigated. Results reveal that appropriate amount of Si₃N₄ particles is required to effectively increase the density of Al₂O₃-SiC_w ceramic composites. The presence of Si₃N₄ particles leads to formation of novel β-sialon phase during hot-press sintering, which effectively enhances fracture toughness and flexural strength of Al₂O₃-SiC_w ceramic composites. It is observed that grain size of newly formed β-sialon phase is extremely sensitive to hot-pressing sintering conditions. The degree of chemical transformation of α-Si₃N₄ into Si_6-zAl_zO_zN_8-z (β-sialon) and z-value of Si_6-zAl_zO_zN_8-z are significantly influenced by sintering temperature. Overall, Al₂O₃-20 vol%SiC_w-15 vol%Si₃N₄ ceramic tool material, with 1.5 vol%Y₂O₃-0.5 vol%La₂O₃-0.5 vol%CeO₂ (YLC) sintering additive, rendered optimal mechanical properties after sintering at 1600 °C under 32 MPa for 30 min. Improved mechanical performance can be ascribed to synergistic toughening and strengthening influence of whiskers and particles.     

Effect of MgF2 addition on mechanical properties and thermal conductivity of silicon nitride ceramics

Dense silicon nitride (Si₃N₄) ceramics were prepared using Y₂O₃ and MgF₂ as sintering aids by spark plasma sintering (SPS) at 1650 °C for 5 min and post-sintering annealing at 1900 °C for 4 h. Effects of MgF₂ contents on densification, phase transformation, microstructure, mechanical properties, and thermal conductivity of the Si₃N₄ ceramics before and after heat treatment were investigated. Results indicated that the initial temperature of liquid phase was effectively decreased, whereas phase transformation was improved as increasing the content of MgF₂. For optimized mechanical properties and thermal conductivity of Si₃N₄, optimum value for MgF₂ content existed. Sample with 3 mol.% Y₂O₃ and 2 mol.% MgF₂ obtained optimum flexural strength, fracture toughness and thermal conductivity (857 MPa, 7.4 MPa m^1/2 and 76 W m⁻¹ K⁻¹, respectively). It was observed that excessive MgF₂ reduced the performance of the ceramic, which was caused by the presence of excessive volatiles.     

ZrSi2–MgO as novel additives for high thermal conductivity of β-Si3N4 ceramics

A novel ZrSi₂–MgO system was used as sintering additive for fabricating high thermal conductivity silicon nitride ceramics by gas pressure sintering at 1900°C for 12 hours. By keeping the total amount of additives at 7 mol% and adjusting the amount of ZrSi₂ in the range of 0-7 mol%, the effect of ZrSi₂ addition on sintering behaviors and thermal conductivity of silicon nitride were investigated. It was found that binary additives ZrSi₂–MgO were effective for the densification of Si₃N₄ ceramics. XRD observations demonstrated that ZrSi₂ reacted with native silica on the Si₃N₄ surface to generate ZrO₂ and β-Si₃N₄ grains. TEM and in situ dilatometry confirmed that the as formed ZrO₂ collaborated with MgO and Si₃N₄ to form Si–Zr–Mg–O–N liquid phase promoting the densification of Si₃N₄. Abnormal grain growth was promoted by in situ generated β-Si₃N₄ grains. Consequently, compared to ZrO₂-doped materials, the addition of ZrSi₂ led to enlarged grains, extremely thin grain boundary film and high contiguity of Si₃N₄–Si₃N₄ grains. Ultimately, the thermal conductivity increased by 34.6% from 84.58 to 113.91 W·(m·K)⁻¹ when ZrO₂ was substituted by ZrSi₂.     

Effect of lattice defects on the thermal conductivity of β-Si3N4

Two types of β-Si₃N₄ were sintered at 1900 °C one for 8 h and the other for 36 h by using Yb₂O₃ and ZrO₂ as sintering additives. The latter specimen was further annealed at 1700 °C for 100 h to promote grain growth. The microstructures of the sintered materials were investigated by SEM, TEM, and EDS. The thermal conductivities of the specimens were 110 and 150 Wm⁻¹K⁻¹, respectively. The sintered material which possessed 110 Wm⁻¹K⁻¹ had numerous small precipitates that consisted of Yb, O and N elements and internal dislocations in the β-Si₃N₄ grains. In the sintered material with 150 Wm⁻¹K⁻¹ neither precipitates nor dislocations were observed in the grains. The microscopic evidence indicates that the improvement in the thermal conductivity of the β-Si₃N₄ was attributable to the reduction of internal defects of the β-Si₃N₄ grains with sintering and annealing time as the grains grew.     

Microstructure evolution of Si3N4 ceramics with high thermal conductivity by using Y2O3 and MgSiN2 as sintering additives

Silicon nitride (Si₃N₄) ceramics were prepared by gas-pressure sintering using Y₂O₃–MgSiN₂ as a sintering additive. The densification behavior, phase transition, and microstructure evolution were investigated in detail, and the relevance between the microstructure and the performance (including thermal conductivity and mechanical properties) was further discussed. A significant change from a bimodal to a homogeneous microstructure and a decreased grain size occurred with increasing Y₂O₃–MgSiN₂ content. When the small quantity of preformed β-Si₃N₄ nuclei grew preferentially and rapidly in a short time, an obvious bimodal microstructure was obtained in the sample with 4 mol% and 6 mol% Y₂O₃–MgSiN₂. When more β-Si₃N₄ nuclei grew at a relatively rapid rate, the sample with 8 mol% Y₂O₃–MgSiN₂ showed a microstructure consisting of numerous abnormally grown β-Si₃N₄ grains and small grains. When more β-Si₃N₄ nuclei grew simultaneously and slowly, there was a homogeneous microstructure and smaller grains in the sample containing 10 mol% Y₂O₃–MgSiN₂. Benefitting from the completely dense, significant bimodal microstructure, low grain boundary phase, and excellent Si₃N₄–Si₃N₄ contiguity, the sample containing 6 mol% Y₂O₃–MgSiN₂ exhibited great comprehensive performance, with a maximum thermal conductivity and fracture toughness of 84.1 W/(m⋅K) and 8.97 MPa m^1/2, as well as a flexural strength of 880.2 MPa.     

A strategy for fabricating textured silicon nitride with enhanced thermal conductivity

C-axis textured Si₃N₄ with a high thermal conductivity of 176 W m⁻¹ K⁻¹ along the grain alignment direction was fabricated by slip casting raw α-Si₃N₄ powder seeded with near-equiaxed β-Si₃N₄ particles and Y₂O₃–MgSiN₂ as sintering additives in a rotating strong magnetic field of 12 T, followed by gas pressure sintering at 1900 °C for 12 h at a nitrogen pressure of 1 MPa. The green material reached a relative density of 57%, with slip casting and the sintered material exhibited a relative density of 99% and a Lotgering orientation factor of 0.98. The morphology of the β-Si₃N₄ seeds had little effect on the texture development and thermal anisotropy of textured Si₃N₄. The technique developed provides highly conductive Si₃N₄ with conductivity to the thickness direction, which is a major advantage in practical use. The technique is also simple, inexpensive and effective for producing textured Si₃N₄ with high thermal conductivity of over 170 W m⁻¹ K⁻¹.     

Phase formation and microstructural evolution of Ca α-sialon using different Si3N4 starting powders

Silicon nitride has two polymorphous structures, α-Si₃N₄ and β-Si₃N₄. In this study three different Si₃N₄ starting powders (∼100%α, 40%α+60%β, ∼100%β) were used to prepare Ca α-sialon with the composition Ca_1.8Si_6.6Al_5.4O_1.8N_14.2 by pressureless sintering. Comparison was made concerning the densification process, reaction sequence and microstructure of the corresponding materials. The sluggish reactivity of β-Si₃N₄ resulted in poorer densification during sintering. All the three starting powders produced a similar final phase assembly, namely α-sialon together with a small amount of AlN and AlN polytypoid except that traces of unreacted β-Si₃N₄ remained until 1800° in samples prepared with ∼100%β-Si₃N₄ powders. Elongated α-sialon grain morphology has been identified in the samples prepared using all the three different Si₃N₄ starting powders. Coarser elongated α-sialon grains with lower aspect ratio were found in samples using higher β phase starting powders.     

Effect of a new nonoxide additive,Y3Si2C2, on the thermal conductivity and mechanical properties of Si3N4 ceramics

Enhancement of the thermal conductivity of silicon nitride is usually achieved by sacrificing its mechanical properties (bending strength). In this study, β-Si₃N₄ ceramics were prepared using self-synthesized Y₃Si₂C₂ and MgO as sintering additives. It was found that the thermal conductivity of the Si₃N₄ ceramics was remarkably improved without sacrificing their mechanical properties. The microstructure and properties of the Si₃N₄ ceramics were analyzed and compared with those of the Y₂O₃-MgO additives. The addition of Y₃Si₂C₂ eliminated the inherent SiO₂ and introduced nitrogen to increase the N/O ratio of the grain-boundary phase, inducing Si₃N₄ grain growth, increasing Si₃N₄ grain contiguity, and reducing lattice oxygen content in Si₃N₄. Therefore, by replacing Y₂O₃ with Y₃Si₂C₂, the thermal conductivity of the Si₃N₄ ceramics was significantly increased by 31.5% from 85 to 111.8Wm⁻¹K⁻¹, but the bending strength only slightly decreased from 704 ± 63MPa to 669 ± 33MPa.     

Investigation on thermal conductivity and mechanical properties of Si3N4 ceramics via one-step sintering

High thermal conductivity Si₃N₄ ceramics were fabricated using a one-step method consisting of reaction-bonded Si₃N₄ (RBSN) and post-sintering. The influence of Si content on nitridation rate, β/(α+β) phase rate, thermal conductivity and mechanical properties was investigated in this work. It is of special interest to note that the thermal conductivity showed a tendency to increase first and then decrease with increasing Si content. This experimental result shows that the optimal thermal conductivity and fracture toughness were obtained to be 66 W (m K)^-1 and 12.0 MPa m^1/2, respectively. As a comparison, the nitridation rate and β/(α+β) phase rate in a static pressure nitriding system, i.e., 97% (MS10), 97% (MS15), 97% (MS20) and 8.3% (MS10), 8.3% (MS15), 8.9% (MS20), respectively, have obvious advantages over those in a flowing nitriding system, i.e., 91% (MS10), 91% (MS15), 93% (MS20) and 3.1% (MS10), 3.3% (MS15), 3.3% (MS20), respectively. Moreover, high lattice integrity of the β-Si₃N₄ phase was observed, which can effectively confine O atoms into the β-Si₃N₄ lattice using MgO as a sintering additive. This result indicates that one-step sintering can provide a new route to prepare Si₃N₄ ceramics with a good combination of thermal conductivity and mechanical properties.     

The effect of fabrication parameters on the mechanical properties of sintered reaction bonded porous Si3N4 ceramics

Porous silicon nitride ceramics were prepared via sintered reaction bonded silicon nitride at 1680 °C. The grain size of nitrided Si₃N₄ and diameter of post-sintered β-Si₃N₄ are controlled by size of raw Si. Porosity of 42.14–46.54% and flexural strength from 141 MPa to 165 MPa were obtained. During post-sintering with nano Y₂O₃ as sintering additive, nano Y₂O₃ can promote the formation of small β-Si₃N₄ nuclei, but the large amount of β-Si₃N₄ (>20%) after nitridation also works as nuclei site for precipitation, in consequence the growth of fine β-Si₃N₄ grains is restrained, the length is shortened, and the improvement on flexural strength is minimized. The effect of nano SiC on the refinement of the β-Si₃N₄ grains is notable because of the pinning effect, while the effect of nano C on the refinement of the β-Si₃N₄ grains is not remarkable due to the carbothermal reaction and increase in viscosity of the liquid phase.