High-strength SiC joints fabricated at a low-temperature of 1400°C using a novel low activation filler of Praseodymium

High-strength SiC joints were successfully obtained by electric current field-assisted sintering technique at a low temperature of 1400°C using a Pr coating (100 nm) as the initial joining filler. A Pr₃Si₂C₂ transient phase was formed in situ by the interfacial reaction, while the eutectic reaction between Pr₃Si₂C₂ and SiC at ∼1150°C resulted in the formation of a liquid phase. The liquid phase promoted the atomic diffusion at the interface and improved consolidation of the newly precipitated nano-sized SiC with the SiC matrix. This led to the formation of partially seamless joints of SiC. When the thickness of the joining layer decreased from 1 to 100 nm, the content of the residual Pr-O phase at the interface decreased, while the bending strength of the joints increased. A sound SiC joint with a bending strength of 227 ± 12 MPa was obtained at such a low temperature as 1400°C when a 100 nm Pr coating was applied.     

Ultrafast low-temperature near-seamless joining of Cf/SiC using a sacrificial Pr3Si2C2 filler via electric current field-assisted sintering technique

A novel layered structure material, Pr₃Si₂C₂, was synthesized at a low temperature of 850 °C using a molten salt approach for the first time, and subsequently used as the joining filler for carbon fibers reinforced SiC composites (C_f/SiC). A robust near-seamless C_f/SiC joint was successfully obtained at 1509 °C (T_i) for 30 s, while an ultrafast heating rate of 6000 °C/min was applied via electric field-assisted sintering technology. The near-seamless joining process was attributed to the newly precipitated SiC grains, which were densified well with the C_f/SiC matrix by liquid-assisted sintering. The liquid phase was in-situ formed by the eutectic reaction between Pr₃Si₂C₂ and SiC. The shear strength of the near-seamless joint obtained at 1509 °C for 30 s was 17.6 ± 3.0 MPa. The failure occurred in the C_f/SiC matrix. The formation of near-seamless C_f/SiC joints dismisses the issues related to thermal mismatch between C_f/SiC matrices and traditional joining fillers.     

Fabrication and characterization of SPS sintered SiC-based ceramic from Y3Si2C2-coated SiC powders

The Y₃Si₂C₂ coating was in-situ synthesized on the surface of SiC powders to form SiC-Y₃Si₂C₂ core-shell structure by using a molten salt technique. Phase diagram calculations on Si-Y-C ternary phase at different temperatures well illustrated that the Y₃Si₂C₂ phase can be stable with SiC but will be in liquid state at 1560?°C. The liquid Y₃Si₂C₂ explained the enhanced consolidation of SiC ceramics and its disappearance after spark plasma sintering. Such Y₃Si₂C₂ coating could not only effectively improve the sintering, but also their mechanical and thermal properties of resultant ceramics. Typically, at 1700?°C, the bulk SiC ceramic presented a mean grain size of 2.5?um and relative density of 99.5% when the molar ratio of Y to SiC is 1:4 in molten salts; the Young’s modulus, indentation hardness and fracture toughness measured by indentation test were 451.7?GPa, 26.3?GPa and 7.9?M?Pam^1/2, respectively; the thermal conductivity is about 145.9?W/(m?K). Excellent thermal and mechanical properties could be associated with the fine grain size, optimized phase composition and improved grain boundary structure.     

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.     

Electrically conductive SiC ceramics processed by pressureless sintering

Polycrystalline SiC ceramics with 10 vol% Y₂O₃-AlN additives were sintered without any applied pressure at temperatures of 1900-2050°C in nitrogen. The electrical resistivity of the resulting SiC ceramics decreased from 6.5 × 10¹ to 1.9 × 10⁻² Ω·cm as the sintering temperature increased from 1900 to 2050°C. The average grain size increased from 0.68 to 2.34 μm with increase in sintering temperature. A decrease in the electrical resistivity with increasing sintering temperature was attributed to the grain-growth-induced N-doping in the SiC grains, which is supported by the enhanced carrier density. The electrical conductivity of the SiC ceramic sintered at 2050°C was ~53 Ω⁻¹·cm⁻¹ at room temperature. This ceramic achieved the highest electrical conductivity among pressureless liquid-phase sintered SiC ceramics.     

Investigation on low-temperature sintered AlN nanoceramics with high thermal conductivity

The aim of this research was to investigate the effect of sintering additive and relatively low-sintering temperature on the thermal conductivity of aluminum nitride nanoceramic. While using nanosized AlN powder and liquid-phase sintering additives, the various sintering processes were performed at temperatures 1400 and 1500°C for several hours. In the analysis methods, thermal conductivity (K) and thermal diffusivity (α) were measured using thermal conductivity analyzer (Hot Disk), scanning electron microscope (SEM) was used to observe the surface morphology of the microstructure, x-ray diffraction analyzer (XRD) to analyze the grain size and crystal structure, Raman spectroscopy (Raman) emission spectrum was analyzed to identify the material microstructure and the densities of AlN specimens were measured by Archimedes method. It was found that the thermal conductivity is related to the densification of nanosize low-temperature sintered material, which can be controlled by additives and sintering temperature. With Y₂O₃ sintering add, the densification of AlN for low-temperature sintering increased by the factor of ～5% to ～12%, and the thermal conductivity was enhanced by 25%. The relative density observed in this research is about 78%-84%, and the thermal conductivity measured is in the range of 9-14 W/mK.     

Transparent polycrystalline MgO ceramic fabricated by low-temperature vacuum sintering with MgF2 additive

This study introduces transparent MgO ceramics produced via simply vacuum sintering at 1200–1500 °C by optimal incorporation of MgF₂ as a sintering additive. The effect of MgF₂ content and sintering temperature on the densification process, optical, and thermal properties of MgO ceramics is presented with emphasis on its function as a sintering aid and adverse effect of MgF₂ evaporation in the condition of high MgF₂ content or high sintering temperature. MgO ceramic with 1.0 mol% MgF₂ sintered at 1300 °C exhibits the highest relative density of 99.95% with average grain size of 17.46 μm. The in-line transmittance attains 60% at 1000 nm and >80% in the infrared range (3.8–6.8 μm), without absorption bands originated from the carbon contamination. The corresponding room-temperature thermal conductivity reaches 47.25 W/(m∙K). These results demonstrate that MgF₂ is an outstanding sintering additive for the preparation transparent MgO ceramics.     

Thermal conductivity of liquid-phase sintered silicon carbide ceramics: A review

Silicon carbide (SiC) exhibits excellent thermal conductivity. Recently, thermal conductivity that amounts to 261.5 W/m-K has been obtained in polycrystalline SiC ceramic liquid-phase sintered (LPS) with Y₂O₃-Sc₂O₃ additives at 2050 °C under a nitrogen atmosphere. From the additive used to the sintering atmosphere selected, many factors affect the thermal conductivity of the SiC. In this review, important factors that are known to determine the thermal conductivity of LPS-SiC (lattice oxygen/nitrogen content, porosity, grain size, grain boundary structure, phase transformation, and additive composition) have been evaluated. While reviewing the impact of each factor on thermal conductivity, hidden correlations among different factors are also discussed. Among the factors that are claimed to be important, we suggest a few factors that are more critical to thermal conductivity than others. Based on the most critical factors on the thermal conductivity of LPS-SiC, a complete engineers’ guide for high thermal conductivity LPS-SiC is proposed.     

A novel combination of precursor pyrolysis assisted sintering and rapid sintering for construction of multi-composition coatings to improve ablation resistance of SiOC ceramic modified carbon fiber needled felt preform composites

A double-layer coating composed of MoSi₂–SiO₂–SiC/ZrB₂–MoSi₂–SiC was designed and successfully constructed by a novel combination of precursor pyrolysis assisted sintering and rapid sintering to improve the ablation resistance of SiOC ceramic modified carbon fiber needled felt preform composites (CSs). The ZrB₂–MoSi₂–SiC inner layer coating was in relatively uniform distribution in the zone of 0–3 mm from the surface of CSs through the slurry/precursor infiltration in vacuum and SiOC precursor pyrolysis assisted sintering, which played a predominant role in improving oxidation and ablation resistance and maintaining the morphology of CSs. The MoSi₂–SiO₂–SiC outer layer coating was prepared by the spray and rapid sintering to further protect CSs from high-temperature oxidation. The ablation resistance of CSs coated with double-layer coating was evaluated by an oxygen-acetylene ablation test under the temperature of 1600–1800 °C with different ablation time of 1000 and 1500 s. The results revealed that the mass recession rates increased with the rise of ablation temperature and extension of ablation time, ranging from 0.47 g/(m²·s) to 0.98 g/(m²·s) at 1600–1800 °C for 1000 s and from 0.72 g/(m²·s) to 0.86 g/(m²·s) for 1000–1500 s at 1700 °C, while the linear recession rates showed negative values at 1700 °C due to the formation of oxides, such as SiO₂ and ZrO₂. The ablation mechanism of the double-layer coating was analyzed and found that a SiO₂–ZrO₂–Mo_4.8Si₃C_0.6 oxidation protection barrier would be formed during the ablation process to prevent the oxygen diffusion into the interior CSs, and this study provided a novel and effective way to fabricate high-temperature oxidation protective and ablation resistant coating.     

High thermal conductivity silicon nitride ceramics prepared by pressureless sintering with ternary sintering additives

Silicon nitride ceramics were pressureless sintered at low temperature using ternary sintering additives (TiO₂, MgO and Y₂O₃), and the effects of sintering aids on thermal conductivity and mechanical properties were studied. TiO₂–Y₂O₃–MgO sintering additives will react with the surface silica present on the silicon nitride particles to form a low melting temperature liquid phase which allows liquid phase sintering to occur and densification of the Si₃N₄. The highest flexural strength was 791(±20) MPa with 12 wt% additives sintered at 1780°C for 2 hours, comparable to the samples prepared by gas pressure sintering. Fracture toughness of all the specimens was higher than 7.2 MPa·m^1/2 as the sintering temperature was increased to 1810°C. Thermal conductivity was improved by prolonging the dwelling time and adopting the annealing process. The highest thermal conductivity of 74 W/(m∙K) was achieved with 9 wt% sintering additives sintered at 1810°C with 4 hours holding followed by postannealing.     

Thermal conductivity of spark plasma sintered SiC ceramics with Alumina and Yttria

In this study, dense SiC ceramics were fabricated at 1650?1750 °C for 10?60 min by spark plasma sintering (SPS) using 3?10 wt.% Al₂O₃-Y₂O₃ as sintering additives. Effects of sintering temperature, sintering additive content and holding time on microstructure as well as correlations between microstructure and thermal conductivity were investigated. An increase in the sintering temperature promotes grain growth. Extending holding time has little influence on grain size but results in formation of continuous network of sintering additive, which increases interfacial thermal resistance and thus decreases thermal conductivity. For SiC ceramics composed of continuous SiC matrix and discrete secondary phase (yttrium aluminum garnet, YAG), an increase in the sintering additive content results in smaller grain size and lower thermal conductivity. The lower thermal conductivity of the SiC ceramic with higher sintering additive content is mainly due to the smaller grain size rather than the low intrinsic thermal conductivity of YAG.     

Low-temperature hot-press sintering of AlN ceramics with MgO–CaO–Al2O3–SiO2 glass additives for ceramic heater applications

Aluminum nitride (AlN) is used a ceramic heater material for the semiconductor industry. Because extremely high temperatures are required to achieve dense AlN components, sintering aids such as Y₂O₃ are typically added to reduce the sintering temperature and time. To further reduce the sintering temperature, in this study, a low-melting-temperature glass (MgO–CaO–Al₂O₃–SiO₂; MCAS) was used as a sintering additive for AlN. With MCAS addition, fully dense AlN was obtained by hot-press sintering at 1500 °C for 3 h at 30 MPa. The mechanical properties, thermal conductivity, and volume resistance of the sintered AlN–MCAS sample were evaluated and compared with those of a reference sample (AlN prepared with 5 wt% Y2O3 sintering aid sintered at 1750 °C for 8 h at 10 MPa). The thermal conductivity of AlN prepared with 0.5 wt% MCAS was 91.2 W/m?K, which was 84.8 W/m?K lower than that of the reference sample at 25 °C; however, the difference in thermal conductivity between the samples was only 14.2 W/m?K at the ceramic-heater operating temperature of 500 °C. The flexural strength of AlN–MCAS was 550 MPa, which was higher than that of the reference sample (425 MPa); this was attributed to the smaller grain size achieved by low-temperature sintering. The volume resistance of AlN–MCAS was lower than that of the reference sample in the range of 200–400 °C. However, the resistivity of the proposed AlN–MCAS sample was higher than that of the reference sample (500 °C) owing to grain-boundary scattering of phonons. In summary, the proposed sintering strategy produces AlN materials for heater applications with low production cost, while achieving the properties required by the semiconductor industry.     

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.     

Improved electrical and thermal properties of silicon oxycarbide/spodumene composites

Novel bulk SiOC/spodumene composites have been developed by spark plasma sintering (SPS) at relatively low temperature (1200–1400 °C). Spodumene is a cheap and natural available lithium aluminosilicate mineral which acts as meltable/active filler. At 1300–1400 °C, the Al migrates toward the glassy matrix producing a Si-Al-O network and the crystallization of α-cristobalite. The C_free phase also experiences a deep transformation. The epitaxial growth of few-layered graphene over SiC particles occurs at 1400 °C. An increase in the phonon transport is observed (36%, 1.28 – 2.14 Wm⁻¹K⁻¹) associated to the reduction of the interface resistance between the partially crystallized SiO₂ matrix and the SiC nano-wires/graphene-like carbon conductive phase. The electrical conductivity increases (1.14 ×10⁻² – 8.1 Sm⁻¹) due to the densification reached and an increasing ordering degree of the tortuous C_free phase with a high quality of interconnection and crystallization. Raman parameters are determinant to understand the thermal and electrical response.     

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.     

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.     

The effect of rare earth oxides on the pressureless liquid phase sintering of α-SiC

Silicon carbide (SiC) ceramics have been fabricated by pressureless liquid phase sintering with Al₂O₃ and rare-earth oxides (Lu₂O₃, Er₂O₃ and CeO₂) as sintering additives. The effect was investigated of the different types of rare earth oxides on the mechanical property, thermal conductivity and microstructure of pressureless liquid phase sintered SiC ceramics. The room temperature mechanical properties of the ceramics were affected by the type of rare earth oxides. The high temperature performances of the ceramics were influenced by the triple junction grain boundary phases. With well crystallized triple junction grain boundary phase, the SiC ceramic with Al₂O₃–Lu₂O₃ as sintering additive showed good high temperature (1300 °C) performance. With clean SiC grain boundary, the SiC ceramic with Al₂O₃–CeO₂ as sintering additive showed good room temperature thermal conductivity. By using appropriate rare earth oxide, targeted tailoring of the demanding properties of pressureless liquid phase sintered SiC ceramics can be achieved.     

Fabrication of lightweight ZrO2 fiberboards using hollow ZrO2 fibers

ZrO₂ fiberboards with ultra-low densities (0.34–0.40 g/cm³) were fabricated using biomorphic ZrO₂ hollow fibers, which have a lower density and better thermal insulation than traditional ZrO₂ solid fibers. The effects of sol binder content, sintering temperature, and proportion of solid fibers on the density, microstructure, compressive strength, linear shrinkage, and thermal conductivity of lightweight ZrO₂ fiberboards were investigated. The results showed that the hollow features of biomorphic ZrO₂ fibers were successfully maintained after they were made into ZrO₂ fiberboards, which made them less dense and thermally conductive. The best conditions were found to be a sol binder content of 30 vol%, sintering temperature of 1400 °C, and 20 wt% sintered solid fibers to balance thermal insulation and compressive strength. The results show that the density and thermal conductivity of lightweight ZrO₂ fiberboard gives it obvious advantages as a heat-insulating ceramic. Specifically, when the sintering temperature was 1400 °C, the sample had an ultra-low density of 0.34–0.40 g/cm³, a thermal conductivity of 0.101–0.116 W/(m·K) (at 500 °C), a compressive strength of 0.05–0.24 MPa, and a linear shrinkage of 9.4–13%.