Development of spark plasma sintered conductive SiC–TiB2 composites for electrical discharge machining applications

Highly dense electrically conductive silicon carbide (SiC)–(0, 10, 20, and 30 vol%) titanium boride (TiB₂) composites with 10 vol% of Y₂O₃–AlN additives were fabricated at a relatively low temperature of 1800°C by spark plasma sintering in nitrogen atmosphere. Phase analysis of sintered composites reveals suppressed β→α phase transformation due to low sintering temperature, nitride additives, and nitrogen sintering atmosphere. With increase in TiB₂ content, hardness increased from 20.6 to 23.7 GPa and fracture toughness increased from 3.6 to 5.5 MPa m^1/2. The electrical conductivity increased to a remarkable 2.72 × 10³ (Ω cm)^–1 for SiC–30 vol% TiB₂ composites due to large amount of conductive reinforcement, additive composition, and sintering in nitrogen atmosphere. The successful electrical discharge machining illustrates potential of the sintered SiC–TiB₂ composites toward extending the application regime of conventional SiC-based ceramics.     

Influence of silicon carbide addition on the microstructural development of hot pressed zirconium and titanium diborides

The influences of adding SiC on the microstructure and densification behavior of ZrB₂ and TiB₂ ceramics, hot pressed at 1850 °C for 60 min under 20 MPa, were investigated. The sintered samples were characterized by SEM, EDS and XRD methods. A fully dense TiB₂-based ceramic was obtained by adding 30 vol% SiC. The grain size of ZrB₂ or TiB₂ matrices in the final microstructures decreased with increasing SiC content. The XRD analyses, microstructural characterization as well as thermodynamical calculations proved the in-situ formation of TiC in the SiC reinforced TiB₂-based composites. The interfaces between ZrB₂ and SiC grains in the SiC reinforced ZrB₂-based composites were free of any impurities or tertiary interfacial phases such as ZrC. This result was consistent with the X-ray diffraction pattern and thermodynamics.     

Effect of temperature on the structure and mechanical properties of SiC–TiB2 composite ceramics by solid-phase spark plasma sintering

SiC composite ceramics have good mechanical properties. In this study, the effect of temperature on the microstructure and mechanical properties of SiC–TiB₂ composite ceramics by solid-phase spark plasma sintering (SPS) was investigated. SiC–TiB₂ composite ceramics were prepared by SPS method with graphite powder as sintering additive and kept at 1700 °C, 1750 °C, 1800 °C and 50 MPa for 10min.The experimental results show that the proper TiB₂ addition can obviously increase the mechanical properties of SiC–TiB₂ composite ceramics. Higher sintering temperature results in the aggregation and growth of second-phase TiB₂ grains, which decreases the mechanical properties of SiC–TiB₂ composite ceramics. Good mechanical properties were obtained at 1750 °C, with a density of 97.3%, Vickers hardness of 26.68 GPa, bending strength of 380 MPa and fracture toughness of 5.16 MPa m^1/2.     

Effects of graphite nano-flakes on thermal and microstructural properties of TiB2–SiC composites

In the last decades, the production of ultra-high temperature composites with improved thermo-mechanical properties has attracted much attention. This study focuses on the effect of graphite nano-flakes addition on the microstructure, densification, and thermal characteristics of TiB₂–25 vol% SiC composite. The samples were manufactured through spark plasma sintering process under the sintering conditions of 1800 °C/7 min/40 MPa. Scanning electron microscopy images demonstrated a homogenous dispersion of graphite flakes within the TiB₂–SiC composite causing a betterment in the densification process. The thermal diffusivity of the specimens was gained via the laser flash technique. The addition of graphite nano-flakes as a dopant in TiB₂–SiC did not change the thermal diffusivity. Consequently, the remarkable thermal conductivity of TiB₂–SiC remained intact. It seems that the finer grains and more interfaces obstruct the heat flow in TiB₂–SiC–graphite composites. Adding a small amount of graphite nano-flakes enhances the densification of the mentioned composite by preventing the grain growth.     

Porous SiC–Si3N4 composite ceramics with excellent EMW absorption property prepared by gelcasting using DMAA

The porous SiC–Si₃N₄ composite ceramics with good EMW absorption properties were prepared by combination of gelcasting and carbothermal reduction. The pre-oxidation of Si₃N₄ powders significantly improved the rheological properties of slurries (0.06 Pa s at 103.92 s⁻¹) and also suppressed the generation of NH₃ and N₂ from Si₃N₄ hydrolysis and reaction between Si₃N₄ and initiator APS, thereby reducing the pore defects in green bodies and enhancing mechanical properties with a maximum value of 42.88 MPa. With the extension of oxidation time from 0 h to 10 h, the porosity and pore size of porous SiC–Si₃N₄ composite ceramics increased from approximately 41.86% and 1.0–1.5 μm to 46.33% and ~200 μm due to the production of CO, N₂ and gaseous SiO, while the sintering shrinkage decreased from 16.24% to 10.50%. With oxidation time of 2 h, the Si₂N₂O fibers formed in situ by the reaction of Si₃N₄ and amorphous SiO₂ effectively enhanced the mechanical properties, achieving the highest flexural strength of 129.37 MPa and fracture toughness of 4.25 MPa m^1/2. Compared with monolithic Si₃N₄ ceramics, the electrical conductivity, relative permittivity and dielectric loss were significantly improved by the in-situ introduced PyC from the pyrolysis of three-dimensional network DMAA-MBAM gel in green bodies and the SiC from the carbothermal reduction reaction between PyC and SiO₂ and Si₃N₄. The porous SiC–Si₃N₄ composite ceramics prepared by the unoxidized Si₃N₄ powders demonstrated the optimal EMW absorption properties with reflection loss of −22.35 dB at 8.37 GHz and 2 mm thickness, corresponding to the effective bandwidth of 8.20–9.29 GHz, displaying great application potential in EMW absorption fields.     

Cutting performance improvement of Si3N4 ceramic cutting tools by adding boride

Cutting performances of silicon nitride (Si₃N₄) ceramic cutting tools with and without boride additive (2.5 vol% ZrB₂ or TiB₂) prepared by hot-pressing at 1500°C were investigated. Due to the α- to β-Si₃N₄ phase transformation and low densification temperature, boride-containing Si₃N₄ ceramics with high hardness and high toughness were obtained. The turning tests showed that the effective cutting lengths of the Si₃N₄–2.5 vol% TiB₂ ceramic (∼2480 m) and Si₃N₄–2.5 vol% ZrB₂ ceramic (∼2200 m) were higher than the monolithic Si₃N₄ ceramic (∼1780 m). As the toughness was improved while maintaining relative high hardness, the cutting performances of the boride-containing Si₃N₄-based inserts were improved by adding 2.5 vol% ZrB₂ or TiB₂. The improved cutting performance indicated that the boride-containing Si₃N₄ ceramics are expected to be used in the field of ceramic cutting tools.     

Effects of TiN content on the properties of hot pressed TiB2–SiC ceramics

This research intended to study the impacts of different contents of the TiN additive on the mechanical properties and microstructural features of the TiB₂–SiC-based composites. Three different samples of TiB₂-15 vol% SiC- x vol% TiN (x = 0, 3.5, and 7) were produced by hot-pressing at 2000 °C under 35 MPa for 120 min. Thanks to advancement of some reactions among the TiB₂ surface oxides and the SiC reinforcement, two in-situ phases of TiC and SiO₂ were produced during the sintering. Nevertheless, the TiN incorporation resulted in generating another in-situ compound (TiC_0.3N_0.7) in the relevant as-sintered ceramics. Moreover, introducing TiN significantly refined the microstructure of the composites, leading to higher mechanical characteristics. Finally, the highest flexural strength (781 MPa) and Vickers hardness (27.1 GPa) values were attained for the sample introduced by 7 vol% TiN.     

Effect of TiB2 addition on grain orientation of porous Si3N4-TiB2 composites by magnetic field alignment technology

Textured porous Si₃N₄-TiB₂ composites were prepared by gel-casting–assisted magnetic field alignment technology and subsequent pressureless sintering in the N₂ atmosphere. The effects of TiB₂ content on grain orientation and properties of composites were studied. Results showed that using the magnetic field of 6T, Si₃N₄ grains exhibited a high a- or b-axis orientation and TiB₂ grains exhibited a high c-axis orientation. In textured green bodies, the increase in TiB₂ content from 0 to 20 wt%, the degree of texture of Si₃N₄ grains showed a slight decrease from 0.78 to 0.71. However, the degree of texture of TiB₂ grains was maintained at about 0.98 regardless of TiB₂ content. After sintering, except for the Si₃N₄ and TiB₂ phases, new TiN and BN phases also appeared in the samples. Additionally, the sintering process promotes grain orientation of Si₃N₄ and TiB₂. Herein, the degree of texture of TiB₂ reached to about 1 regardless of TiB₂ content, meaning that the complete grain orientation formed for TiB₂. Owing to the reconstruction reaction between TiB₂ and N₂, new TiN and BN phases did not form the orientation. The increase in TiB₂ contents gradually increased the apparent porosity of the textured samples from 27.9% to 39.4%, thereby leading to the decrease in bending strength from 126.8 ± 18.8 MPa to 60.3 ± 11.2 MPa and from 105.3 ± 19.8 MPa to 53.6 ± 13.0 MPa in two directions, respectively.     

Effects of Al2O3–Y2O3/Yb2O3 additives on microstructures and mechanical properties of silicon nitride ceramics prepared by hot-pressing sintering

Silicon nitride (Si₃N₄) ceramics doped with two different sintering additive systems (Al₂O₃–Y₂O₃ and Al₂O₃–Yb₂O₃) were prepared by hot-pressing sintering at 1800℃ for 2 h and 30 MPa. The microstructures, nano-indentation test, and mechanical properties of the as-prepared Si₃N₄ ceramics were systematically investigated. The X-ray diffraction analyses of the as-prepared Si₃N₄ ceramics doped with the two sintering additives showed a large number of phase transformations of α-Si₃N₄ to β-Si₃N₄. Grain size distributions and aspect ratios as well as their effects on mechanical properties are presented in this study. The specimen doped with the Al₂O₃–Yb₂O₃ sintering additive has a larger aspect ratio and higher fracture toughness, while the Vickers hardness is relatively lower. It can be seen from the nano-indentation tests that the stronger the elastic deformation ability of the specimens, the higher the fracture toughness. At the same time, the mechanical properties are greatly enhanced by specific interlocking microstructures formed by the high aspect ratio β-Si₃N₄ grains. In addition, the density, relative density, and flexural strength of the as-prepared Si₃N₄ ceramics doped with Al₂O₃–Y₂O₃ were 3.25 g/cm³, 99.9%, and 1053 ± 53 MPa, respectively. When Al₂O₃–Yb₂O₃ additives were introduced, the above properties reached 3.33 g/cm³, 99.9%, and 1150 ± 106 MPa, respectively. It reveals that microstructure control and mechanical property optimization for Si₃N₄ ceramics are feasible by tailoring sintering additives.     

Preparation and Performance Study of Sialon‐Si3N4‐SiC Composite Ceramics for Concentrated Solar Power

For lowering the sintering temperature of silicon carbide ceramics used for solar thermal energy storage technology, O'‐Sialon and silicon nitride were employed as composite phases to construct Sialon‐Si₃N₄‐SiC composite ceramics. The composite ceramics were synthesized using SiC, Si₃N₄, quartz, and different alumina sources as starting materials with noncontact graphite‐buried sintering method. Influences of alumina sources on the physical properties and thermal shock resistance of the composites were studied. The results revealed that the employment of O'‐Sialon and silicon nitride could decrease the sintering temperature greatly to 1540°C. The optimum formula G2 prepared from mullite as alumina source achieved the best performances: 66.7 MPa of bending strength, 10.0 W/(m·K) of thermal conductivity. The composition parameter x = 0.4 of O'‐Sialon decreased to 0.04 after 30 cycles thermal shock, and the bending strength increased with a rate of 11.0% due to the increase of O'‐Sialon grain size, and the optimization of microstructure caused by the transformation of O'‐Sialon grains and densification within the samples. The good thermal shock resistance makes the composites suitable for the use as thermal storage materials of concentrated solar power generation.     

Fabrication of continuously porous SiC–Si3N4 composite using SiC powder by extrusion process

Large amounts of waste SiC sludge containing small amounts of Si and organic lubricant were produced during the wire cutting process of single crystal silicon ingots. Waste SiC sludge was purified by washing it with organic solvent and purified SiC powder was used to fabricate the continuously porous SiC–Si₃N₄ composites, using an extrusion process, in which carbon, 6 wt% Y₂O₃ + 2 wt% Al₂O₃ and ethylene vinyl acetate were added as a pore-forming agent, sintering additives and binder, respectively. In the burning-out process, the binder and carbon were fully removed and continuously porous SiC–Si₃N₄ composites were successfully fabricated. The green bodies containing waste SiC, Si powder and sintering additives were nitrided at 1400 °C in a flowing N₂ + 10% H₂ gas mixture. The continuously porous composites contained SiC, α-Si₃N₄, β-Si₃N₄ and few Fe phases. The pore size of the second passed and third passed SiC–Si₃N₄ composites was 260 μm and 35 μm in diameter, respectively. The values of bending strength and hardness in the second passed and third passed samples were 62.97 MPa, 388 Hv and 77.82 MPa, 423 Hv, respectively.     

On the fabrication and mechanical properties of Si3N4 ceramics with low content sintering additives

Si₃N₄ ceramics were prepared by hot pressing (HP) and spark plasma sintering (SPS) methods using low content (5 mol%) Al₂O₃–RE₂O₃(RE = Y, Yb, and La)–SiO₂/TiN as sintering additives/secondary additives. The effects of sintering additives and sintering methods on the composition, microstructures, and mechanical properties (hardness and fracture toughness) were investigated. The results show that fully density Si₃N₄ ceramics could be fabricated by rational tailoring of sintering additives and sintering method, and TiN secondary additive could promote the density during HP and SPS. Besides, SN-AYS-SPS possesses the most competitive mechanical properties among all the as-prepared ceramics with the Vickers hardness as 17.31 ± .43 GPa and fracture toughness as 11.07 ± .48 MPa m^1/2.     

Hot-pressing and characterization of TiB2–SiC composites with different amounts of BN additive

This research aimed to study the influence of different amounts of hBN additive on the mechanical properties and microstructure of TiB₂-15 vol% SiC samples. All ceramics, containing 0, 3.5, and 7 vol% hBN, were sintered at 2000 °C using a hot-pressing route and reached their near full densities. Thanks to two different chemical reactions among the SiC reinforcement and the TiB₂ surface oxides (B₂O₃ and TiO₂), the in-situ phases of SiO₂ and TiC were generated over the sintering process. The intergranular mode was identified as the predominant fracture type in all three composite samples. The hBN additive could contribute to grain refining of composites so that the sample containing 7 vol% hBN reached the finest microstructure. Finally, the highest Vickers hardness of 25.4 HV_0.5 kg and flexural strength of 776 MPa were attained for the TiB₂–SiC and TiB₂–SiC-7 vol% hBN samples, respectively.     

Preparation of TiB2–SiC composites toughened with interlocking microstructure by self-assembled TiB2 plates

The spark plasma sintering (SPS) technique was found to effectively improve the mechanical properties of TiB₂–SiC ceramic by forming a unique interlocking structure. This study investigated the phase transition process of the hexagonal micro-platelets TiB₂ powders with self-assembled structure during the molten-salt-mediated carbothermal reduction and its effect on promoting the mechanical properties of TiB₂-based ceramics. It was found that the SPS approach ensured a highly densified TiB₂–SiC ceramics with enhanced Vickers hardness of 21.0 ± 1.3 GPa and fracture resistance of 7.8 ± 0.3 MPa m^1/2. The performance enhancement of the resultant TiB₂–SiC composite was attributed to the interlocking structure from the original anisotropic TiB₂ powders, which could effectively absorb the energy and facilitate the crack deflection.     

A Novel Si3N4–SiC Ceramic Used for Volumetric Receivers

Si₃N₄–SiC composite ceramics used for volumetric receivers were fabricated by pressureless sintering of micrometer SiC, Si₃N₄, andalusite, and other minor additions powders. Mechanical, thermal expansion, thermal conductivity, and thermal shock resistance properties were tested at different sintering temperatures. The best sintering temperature of optimum formula A2 is 1360°C, and the bending strength reaches 79.60 Mpa. And moreover, its thermal expansion coefficient is 6.401 × 10^?6/°C, thermal conductivity is 7.83 W/(m K), and no crack occurs even subjected to 30 cycles thermal shock with a bending strength increase rate of 4.72%. X‐ray diffraction results show that the phase constituents of the sintered products mainly consist of SiC, Si₃N₄, mullite, and quartz. Microstructure that is most appropriate and exhibits maximal thermal shock resistance was detected using SEM. The porosity of Si₃N₄–SiC ceramic foam prepared from formula A2 is 95%, which provides a rapid and steady action for the receiver. The evaluation of the present foam shows that Si₃N₄–SiC ceramic composite is a good candidate for volumetric receivers.     

Fabrication of Si3N4–SiC/SiO2 composites using 3D printing and infiltration processing

Si₃N₄–SiC/SiO₂ composites were prepared by employing three-dimensional (3D) printing using selective laser sintering (SLS) and infiltration processing. The process was based on the infiltration of silica sol into porous SLS parts, and silicon carbide and silicon nitride particles were bonded by melted nano-sized silica particles. To optimize the manufacturing process, the phase compositions, microstructures, porosities, and flexural strengths of the Si₃N₄–SiC/SiO₂ composites prepared at different heat-treatment temperatures and infiltration times were compared. Furthermore, the effects of the SiC mass fraction and the addition of Al₂O₃ and mullite fibers on the properties of the Si₃N₄–SiC/SiO₂ composites were investigated. After repeated infiltration and heat treatment, the flexural strength of the 3D-printed Si₃N₄–SiC/SiO₂ composite increased significantly to 76.48 MPa. Thus, a Si₃N₄–SiC/SiO₂ composite part with a complex structure was successfully manufactured by SLS and infiltration processes.     

Effects of SiC amount and morphology on the properties of TiB2-based composites sintered by hot-pressing

This investigation intended to assess the influence of SiC morphology on the sinterability and physical-mechanical features of TiB₂-SiC composites. For this aim, different volume percentages of SiC particles and SiC whiskers were introduced to TiB₂ samples hot-pressed at 1950 °C for 2 h under an external pressure of 25 MPa. The characterization of as-sintered specimens was carried out using X-ray diffraction, optical microscopy, and scanning electron microscopy. The relative density studies revealed that SiC_w had a more significant impact on the sinterability of TiB₂-based composites. The XRD investigation confirmed the production of an in-situ TiC phase during the hot-pressing; however, some peaks related to the graphitized carbon also appeared in the patterns of SiC_w-doped ceramics. The addition of 25 vol% SiC_p halved the average grain size of TiB₂ while introducing the same content of SiC_w decreased this value by just around 20%. Finally, the highest Vickers hardness and fracture toughness were obtained for the sample reinforced with 25 vol% SiC_w, standing at 29.3 GPa and 6.1 MPa m^1/2, respectively.     

The fabrication of tungsten reinforced silicon nitride ceramics by altering nitrogen pressure

Due to high ductility, high-temperature melting, low thermal expansion coefficient, etc., tungsten (W) might be considered to be an ideal reinforcement in toughening or strengthening Si₃N₄ ceramics. However, it is difficult to fabricate W/Si₃N₄ composites due to the possible reactions between W and Si₃N₄ during sintering process at the high temperature. In this work, a novel way to avoid the reactions and fabricate the W/Si₃N₄ composites was proposed by thermodynamic analysis and verified by experiment. Firstly, the phase equilibrium between W and Si₃N₄ as a function of temperature and nitrogen pressure was thermodynamically calculated, which indicates that one critical nitrogen pressure exists for reactions between W and Si₃N₄ at a certain temperature. As the nitrogen pressure is higher than the critical value, the reactions would be inhibited or adversely proceeded. Based on the results, W was innovatively in-situ introduced in the form of WSi₂ after sintering at 1750?°C under 50?bar nitrogen pressure. Moreover, the fracture toughness of Si₃N₄ ceramics was enhanced from 7.1?±?0.2 to 8.0?±?0.4?MPa?m^1/2, which proposes a new reinforcement or method in toughening Si₃N₄ ceramics.     

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.     

Fabrication and contact resistivity of W–Si3N4/TiB2–Si3N4/p–SiGe thermoelectric joints

The design and fabrication of silicon germanium (SiGe) thermoelectric elements, typically including the selection of electrode and intermediate materials, the process of joining electrode and intermediate layer onto thermoelectric materials, are the major challenge for SiGe thermoelectric device technology. In this study, W–Si₃N₄ and TiB₂–Si₃N₄ composites are designed as the electrode and intermediate layer, respectively, and the W–i₃N₄/TiB₂–Si₃N₄/p–Si₈₀Ge₂₀B_0.6 joints are fabricated by a one-step spark plasma sintering process. The influences of the composition of TiB₂–Si₃N₄ intermediate layer on the interfacial structure, contact resistivity and interfacial thermal stability are investigated. The interfacial thermal stability is improved with increasing Si₃N₄ content in TiB₂–Si₃N₄ intermediate layer due to the reduced mismatch of coefficients of thermal expansion between the intermediate layer and SiGe. On the other hand, the contact resistivity increases with the rising of Si₃N₄ content due to the weakened TiB₂/SiGe ohmic contact, which degrades the device efficiency. As the balanced point, the intermediate layer with the composition of 80 vol% TiB₂+20 vol% Si₃N₄ provides good interfacial thermal stability and moderately small contact resistivity (~75 μΩ cm² after aging at 1000 °C for 120 h) simultaneously, which is an optimized intermediate layer composition for W–Si₃N₄/TiB₂–Si₃N₄/p–Si₈₀Ge₂₀B_0.6 thermoelectric element. The TiB₂–Si₃N₄ intermediate layer has excellent chemical stability to both W–Si₃N₄ electrode and SiGe thermoelectric material at high temperatures, which contributes to the sharp interface of the joint and effectively prevents the inter-diffusion between the electrode and the SiGe.