Effect of LaB6 addition on compressive creep behavior with simultaneous oxide scale growth of spark plasma sintered ZrB2-SiC composites

A study has been carried out to examine the effect of LaB₆ addition on the compressive creep behavior of ZrB₂-SiC composites at 1300–1400°C under stresses between 47 and 78 MPa in laboratory air. The ZrB₂-20 vol% SiC composites containing LaB₆ (10% in ZSBCL-10 and 14% in ZSBCL-14) besides 5.6% B₄C and 4.8% C as additives were prepared by spark plasma sintering at 1600°C. Due to cleaner interfaces and superior oxidation resistance, the ZSBCL-14 composite has exhibited a lower steady-state creep rate at 1300°C than the ZSBCL-10. The obtained stress exponent (n ∼ 2 ± 0.1) along with cracking at ZrB₂ grain boundaries and ZrB₂-SiC interfaces are considered evidence of grain boundary sliding during creep of the ZSBCL-10 composite. However, the values of n ∼ 1 and apparent activation energy ∼700 kJ/mol obtained for the ZSBCL-14 composite at 1300–1400°C suggest that ZrB₂ grain boundary diffusion is the rate-limiting mechanism of creep. The thickness of the damaged outer layer containing cracks scales with temperature and applied stress, indicating their role in facilitating the ingress of oxygen causing oxide scale growth. Decreasing oxidation-induced defect density with depth to a limit of ∼280 μm, indicates the predominance of creep-based deformation and damage at the inner core of samples.     

The densification behavior,microstructure, mechanical,and thermionic emission properties of LaB6-SiC composite

The LaB₆-SiC composite with the different SiC content (0, 15, 30, 36, 50, 90, and 100 wt.%,) was densified by spark plasma sintering. The effects of SiC content on the densification behavior, microstructure, mechanical, and thermionic emission properties of LaB₆-SiC composite were systemically investigated. The results show that all the rapid shrinkage occurred at the heating stage during densification, and LaB₆-36 wt.%SiC composite owned the maximum shrinkage rate of 1.5 mm/min at T = 1798°C. The highest relative density of the composite decreased from 98.18% to 95.01% as the SiC content increased from 15 wt.% to 90 wt.%, under which the morphology of LaB₆ grain evaluated from the equiaxed to elongated structure, and LaB₆ grain size varied in the range of 5.05–11.42 μm. The similar eutectic structures were observed in the LaB₆-36 wt.% SiC composite because of some LaB₆ grains melting. Both the highest fracture toughness of 5.15 ± 0.56 MPa.m^1/2 and the highest bending strength of 313 ± 4.7 MPa belonged to the LaB₆-36 wt.% SiC composite, which also exhibited thermionic emission current density of 10.74 A/cm² and work function of 2.99 eV at T = 1873 K.     

Consolidation and high-temperature strength of monolithic lanthanum hexaboride

In this study we explored the densification, microstructure evolution, and high-temperature properties of bulk lanthanum hexaboride. LaB₆ bulks were consolidated using spark-plasma sintering only in the temperature range between 1400°C and 1700°C. We adopted flash spark plasma sintering (SPS) of LaB₆ using a direct current heating without a graphite die. We observed a peculiar grain-size gradient when coarse grains exceeding 300 μm were observed on the top side of the specimen, while the bottom side had a grain size of 15–20 μm. Such large grain was not observed using SPS at 2000°C, suggesting that these might originate from a local overheating. Based on the three-point flexural tests, it was observed that the toughness and strength of the LaB₆ were acceptable at room-temperature (3.1 ± 0.2 MPa m^1/2, 300 ± 20 MPa). However, at 1600°C, these parameters would decrease to 1.3 ± 0.1 MPa m^1/2 and 120 ± 40 MPa, respectively.     

Spark plasma sintering of LaB6-(Ti,Zr)B2 composites

The LaB₆-(Ti_, Zr)B₂ composite was fabricated from LaB₆, TiB₂ and ZrB₂ powders by spark plasma sintering (SPS) at 1600–1900°C holding for 5?min under 40?MPa. The densification behaviour, microstructure, mechanical properties were investigated. The complete solid solution phase of (Ti, Zr)B₂ was identified. The morphologies of LaB₆ and (Ti, Zr)B₂ grains were equiaxed and elongated, respectively. The highest relative density of 98.43% and Vickers hardness of 19.56?GPa were obtained at 1900°C. The fracture toughness of 4.43?MPa?m^1/2 was obtained at 1800°C.     

Effect of Si3N4 Addition on Compressive Creep Behavior of Hot‐Pressed ZrB2–SiC Composites

Compressive creep studies have been carried out on hot‐pressed ZrB₂–SiC (ZS) and ZrB₂–SiC–Si₃N₄ (ZSS) composites in air under stress and temperature ranges of 93–140 MPa and 1300°C–1425°C, respectively for time durations of ≈20–40 h. The results of these studies have shown the creep resistance of ZS composite to be greater than that of ZSS. As the temperature is increased from 1300°C to 1425°C, the stress exponent of ZS decreases from 1.7 to 1.1, whereas that of ZSS drops from 1.6 to 0.6. The activation energies for these composites have been found as ≈95 ± 32 kJ/mol at temperatures ≤1350°C, and as ≈470 ± 20 kJ/mol in the range of 1350°C–1425°C. Studies of the postcreep microstructures using scanning and transmission electron microscopy have shown the presence of glassy film with cracks at both ZrB₂ grain boundaries and ZrB₂–SiC interfaces. These results along with calculated values of activation volumes suggest grain‐boundary sliding as the major damage mechanism, which is controlled by O^2? diffusion through SiO₂ at ≤1350°C, and by viscoplastic flow of the glassy interfacial film at temperatures ≥1350°C. Studies by transmission electron microscopy have shown formation of crystalline precipitates of Si₂N₂O near ZrB₂–SiC interfaces in ZSS tested at ≥1400°C, which along with stress exponent values <1 suggests that grain‐boundary sliding involving solution‐precipitation‐type mechanism is operative at these temperatures.     

Reaction,densification, and mechanical properties of Ti2AlCx ceramics at low applied pressure and temperature

Ti₂AlC_x ceramic was produced by reactive hot pressing (RHP) of Ti:Al:C powder mixtures with a molar ratio of 2:1:1–.5 at 10–20 MPa, 1200–1300°C for 60 min. X-ray diffraction analysis confirmed the Ti₂AlC with TiC, Ti₃Al as minor phases in samples produced at 10–20 MPa, 1200°C. The samples RHPed at 10 MPa, 1300°C exhibited ≥95 vol.% Ti₂AlC with TiC as a minor phase. The density of samples increased from 3.69 to 4.04 g/cm³ at 10 MPa, 1200°C, whereas an increase of pressure to 20 MPa resulted from 3.84 to 4.07 g/cm³ (2:1:1 to 2:1:.5). The samples made at 10 MPa, 1300°C exhibited a density from 3.95 to 4.07 g/cm³. Reaction and densification were studied for 2Ti–Al–.67C composition at 10 MPa, 700–1300°C for 5 min showed the formation of Ti–Al intermetallic and TiC phases up to 900°C with Ti, Al, and carbon. The appearance of the Ti₂AlC phase was ≥1000°C; further, as the temperature increased, Ti₂AlC peak intensity was raised, and other phase intensities were reduced. The sample made at 700°C showed a density of 2.87 g/cm³, whereas at 1300°C it exhibited 3.98 g/cm³; further, soaking for 60 min resulted in a density of 4.07 g/cm³. Microhardness and flexural strength of Ti₂AlC_0.8 sample were 5.81 ± .21 GPa and 445 ± 35 MPa.     

Fabricating toughened super-hard B4C composites at lower temperature by transient liquid-phase assisted spark plasma sintering with MoSi2 additives

Toughened, super-hard B₄C triplex-particulate composites were densified by spark plasma sintering with MoSi₂ additives (5, 10, and 15 vol.%) at temperatures in the range 1750–1850 °C at which the reference monolithic B₄C ceramics are porous. It is proved that MoSi₂ is a reactive sintering additive that promotes densification by transient liquid-phase sintering, thus yielding fully-dense B₄C-MoB₂-SiC composites at relatively lower temperatures. Specifically, the MoSi₂ first reacts at moderate temperatures (<1150 °C) with part of B₄C to form MoB₂, SiC, and Si. This last is a transient component that eventually melts (at ～1400 °C), contributing to densification by liquid-phase sintering, and then (at 1500–1700 °C) reacts with free C present in the B₄C starting powders to form more SiC, after which densification continues by solid-state sintering. It is found that these B₄C-MoB₂-SiC composites are super-hard (～30 GPa), tough (～3–4 MPa m^1/2), and fine-grained, a combination that renders them very appealing for structural applications. Finally, research opportunities are discussed for the future microstructural design of a novel family of toughened, ultra-hard/super-hard multi-particulate composites based on B₄C plus refractory borides and carbides.     

Uniaxial plastic deformation in the zirconia-based nanocrystalline ceramics containing a silicate glass

Nanocrystalline yttria-stabilized tetragonal zirconia polycrystal (nc-Y-TZP) powders coated with silicate based glasses were cold isostatically pressed and sintered near to the full density (98–99%). Two glasses with different compositions were used: 93 SiO₂–1 Na₂O–6 SrO (mol%) (designated as SNS glass) and 58 SiO₂–29 Al₂O₃–13 SrO (designated as SAS glass). Uniaxial compression tests of the pure (glass-free) nc-Y-TZP samples yielded strain rates as high as 2·10⁻⁴ s⁻¹ under 60 MPa at 1300 °C. Comparable strain rates were measured in the SNS glass-containing samples, with the maximum of 3·10⁻⁴ s⁻¹ at 1300 °C under a stress of 80 MPa (5 vol.% SNS glass content). Compression tests under 100 MPa exhibited relatively high strain rates of 5·10⁻⁴ and 10⁻⁴ at 1300 °C and 1200 °C, respectively, in the 15 vol.% SAS glass samples. The strain rates measured in the SAS glass-containing samples were achieved at temperatures lower by 100 °C compared to the similar strain rates in the glass-free and SNS glass-containing samples. The microstructure of the deformed samples was similar to that of samples before deformation, within which the ultrafine and equiaxed character of the grains was preserved. Clear evidence for cooperative grain boundary sliding was observed in the SAS glass-containing samples.     

Newly developed cordierite–zircon composites

Abstract

Cordierite-zircon ceramic composites were fabricated by die pressing a commercial cordierite powder with the addition of up to 10 wt-% zircon (ZrSiO₄). Sintering of cordierite was enhanced by the ZrSiO₄ addition through glass phase formation. With ZrSiO₄ additions above 2·5 wt-% no further effect on the mechanical properties of the composites was observed. The maximum flexural strength at 2·5 wt-%ZrSiO₄ addition was 84±7 MPa, about 30% higher than the 67±5 MPa found for pure cordierite. The strength of cordierite at 2·5 wt-%ZrSiO₄ increased with sintering temperature up to 1300°C, owing to the enhanced densification. Above 1300°C, however, the strength was reduced as a result of the formation of large pockets of glassy phase. The average fracture toughness of cordierite was increased from 1·0 to 1·5 MPa m^1/2 with the addition of ZrSiO . This toughening can be attri4 buted to crack deflection around ZrSiO₄ particles rather than to residual compressive stresses imposed on the cordierite owing to thermal expansion mismatch between cordierite and the ZrSiO₄ second phase.     

Densification,mechanical, and tribological properties of ZrB2-ZrCx composites produced by reactive hot pressing

ZrB₂-ZrC_x composites were produced using Zr:B₄C powder mixtures in the molar ratios of 3:1, 3.5:1, 4:1, and 5:1 by reactive hot pressing (RHP) at 4-7 MPa, 1200°C for 60 minutes. X-ray diffraction analyses confirmed the formation of nonstoichiometric zirconium carbide (ZrC_x) with different lattice parameters and enhanced carbide formation by increasing the Zr mole fraction. An increase in applied pressure from 4 to 7 MPa was responsible for the improved relative density (RD) of 4Zr:B₄C composition from 86% to 99%. Microstructural studies on Zr-rich composites showed a reduction in unreacted B₄C particles and enriched elongated ZrB₂ platelets. Reaction and densification mechanism in 4Zr:B₄C composition were studied as a function of temperature increased from 600 to 1200°C at an applied constant pressure of 7 MPa. After 1000°C, <40 vol.% of unreacted Zr was observed during the densification process. Concurrently, low energies of carbon diffusion and carbon vacancy formation were found to enhance nonstoichiometric ZrC_x formation, which was found to be responsible for the completion of the reaction. The plastic deformation of unreacted Zr was responsible for the densification of the ZrB₂-ZrC_x composite. The results clearly showed that the applied pressure is five times lower than the reported values. Moreover, a temperature of 1200°C was sufficient to produce dense ZrB₂-ZrC_x composites. The improved microhardness, flexural strength, fracture toughness, and specific wear rate were 8.2-15 GPa, 265-590 MPa, 2.82-6.33 MPa.m^1/2, and 1.43-0.376 × 10⁻² mm²/N, respectively.     

Development of microstructure during creep of polycrystalline mullite and a nanocomposite mullite/5 vol.% SiC

The microstructures of as-sintered and creep tested polycrystalline mullite and mullite reinforced with 5 vol.% nano-sized SiC particles have been characterized by scanning and transmission electron microscopy. The dislocation densities after tensile creep testing at 1300 and 1400 °C were virtually unchanged as compared to the as-sintered materials which indicates diffusion-controlled deformation. Mullite matrix grain boundaries bending around intergranular SiC particles suggest that grain boundary pinning, in addition to a reduced mullite grain size, contributed to the increased creep resistance of the mullite/5 vol.% SiC nanocomposite. Both materials showed pronounced cavitation at multi-grain junctions after creep testing at 1400 °C which suggests that unaccommodated grain boundary sliding, facilitated by softening of the intergranular glass, occurred at this temperature. This is consistent with the higher stress exponents at 1400 °C.     

Tensile creep properties and damage mechanisms of 2D-SiCf/SiC composites reinforced with low-oxygen high-carbon type SiC fiber

Tensile creep properties of 2D-SiC_f/SiC composites reinforced with low-oxygen high-carbon type SiC fibers were studied in vacuum at 1300°C∼1430°C. The fracture morphology was observed by scanning electron microscopy and the damage of fiber in 2D-SiC_f/SiC composites was characterized by nanoindentation. Moreover, the microstructure of the composite was investigated by high-resolution transmission electron microscopy. The results show that rupture time is much shortened and steady-state creep rate increase three orders of magnitude when creep temperature is higher than 1400°C. There are two different creep damage mechanisms due to the decrease of interfacial bonding strength at high temperature. The amorphous SiO_xC_y phase in the fibers can crystallize into SiC and C and the SiC grain grows in the fiber. The microstructural changes lead to the decrease of fiber strength and degrade the creep properties of the composite above 1400°C.     

Microstructural evolution,mechanical and thermal properties of LaB6 embedded in Si-B-C-N prepared by spark plasma sintering

Si-B-C-N monoliths with 5 wt% LaB₆ additives were prepared by spark plasma sintering at 1250–2000 °C and 50 MPa using a mechanically alloyed mixture of graphite, c-Si, h-BN and LaB₆ powders as the starting materials. Microstructural evolution, mechanical and thermal properties of the as-prepared La/Si-B-C-N monoliths were investigated. The densification of the ceramics starts at 1160° and ends at 1800 °C with the formation of La-containing compounds coupled with SiC and BN(C) phases. La-containing BN(C) grains develop into a lamellar structure at 1900 °C offering improved fracture toughness and decreased Vickers hardness, flexural strength and elastic modulus. The formation of lamellar BN(C) is also responsible for a high thermal expansion coefficient of 4.2×10⁻⁶ /°C.     

Microstructures and mechanical properties of high-entropy (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C ceramics with the addition of SiC secondary phase

The relationships between microstructures and mechanical properties especially strength and toughness of high-entropy carbide based ceramics are reported in this article. Dense (Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C (HEC) and its composite containing 20 vol.% SiC (HEC-20SiC) were prepared by spark plasma sintering. The addition of SiC phase enhanced the densification process, resulting in the promotion of the formation of the single-phase high-entropy carbide during sintering. The high-entropy carbide phase demonstrated a fast grain coarsening but SiC particles remarkably inhibited this phenomena. Dense HEC and HEC-20SiC ceramics sintered at 1900 °C exhibits four-point bending strength of 332 ± 24 MPa and 554 ± 73 MPa, and fracture toughness of 4.51 ± 0.61 MPa·m^1/2 and 5.24 ± 0.41 MPa·m^1/2, respectively. The main toughening mechanism is considered to be crack deflection by the SiC particles.     

Reactive sintering behavior and enhanced densification of (Ti,Zr)B2–(Zr,Ti)C composites

Reactive hot pressing was used to prepare (Ti,Zr)B₂–(Zr,Ti)C composites from equimolar ZrB₂ and TiC powders. The reaction and solid-solution coupling effect and enhanced densification in ZrB₂-50 mol.% TiC were proposed as contrasted to conventional consolidation of TiB₂-50 mol.% ZrC. The (Ti,Zr)B₂–(Zr,Ti)C composite sintered at a temperature as low as 1750 °C exhibited negligible porosity and average grain sizes of 0.30 μm for (Ti,Zr)B₂ and 0.36 μm for (Zr,Ti)C. Complete reaction and rapid densification of ZrB₂-50 mol.% TiC was achieved at 1800 °C for only 10 min. The densification mechanism was mainly attributed to material transport through lattice diffusion of Ti and Zr atoms with an activation energy of 531 ± 16 kJ/mol. This study revealed for the first time novel insights into rapid densification of refractory fine-grained diboride–carbide composites by reactive hot pressing at relatively low temperatures.     

SiC/Si3N4 nano/micro-composite — processing,RT and HT mechanical properties

Two SiC/Si₃N₄ nano/micro composites were prepared from a starting mixture of crystalline α-Si₃N₄, amorphous SiNC, Y₂O₃ and/or Al₂O₃. The composite material for room temperature (RT) application has high strength of 1200 MPa, Weibull modulus of 19 and moderate fracture toughness of 7 MPa m^1/2. The composite for high temperature (HT) application, without Al₂O₃ has RT strength of 710 MPa and is able to keep 60% of its RT strength up to 1300°C. The creep resistance of composite material is approx. 1 order higher compared to relative monolith up to 1400°C.     

Mechanical,thermal, and dielectric properties of SiCf/SiC composites reinforced with electrospun SiC fibers by PIP

Electrospun unidirectional SiC fibers reinforced SiC_f/SiC composites (e-SiC_f/SiC) were prepared with ∼10% volume fraction by polymer infiltration and pyrolysis (PIP) process. Pyrolysis temperature was varied to investigate the changes in microstructures, mechanical, thermal, and dielectric properties of e-SiC_f/SiC composites. The composites prepared at 1100 °C exhibit the highest flexural strength of 286.0 ± 33.9 MPa, then reduced at 1300 °C, mainly due to the degradation of electrospun SiC fibers, increased porosity, and reaction-controlled interfacial bonding. The thermal conductivity of e-SiC_f/SiC prepared at 1300 °C reached 2.663 W/(m∙K). The dielectric properties of e-SiC_f/SiC composites were also investigated and the complex permittivities increase with raising pyrolysis temperature. The e-SiC_f/SiC composites prepared at 1300 °C exhibited EMI shielding effectiveness exceeding 24 dB over the whole X band. The electrospun SiC fibers reinforced SiC_f/SiC composites can serve as a potential material for structural components and EMI shielding applications in the future.     

Strong ZrC ceramics at high temperatures with the addition of W

The effect of W addition on densification, microstructure, and mechanical properties of ZrC ceramics was investigated. W reacted with carbon in ZrC to form WC, which resulted in the formation of ZrC_1-x at 1300-1700°C, while WC was further dissolved in ZrC to form a (Zr_1-yW_y)C_1-x solid solution at 1800-2000°C. The relative density of ZrC with 5 mol% W (ZW5, 96.8%) was markedly higher than that of pure ZrC (Z0, 94.8%). ZW5 exhibited a fine homogeneous microstructure with a grain size (2.6 ± 0.5 μm) much smaller than that of Z0 (10.9 ± 3.0 μm), while excess W addition (10 mol%) in ZrC adversely affected the densification and the microstructure. The flexure strength of Z0 was 446 ± 46 MPa at room temperature, which almost linearly decreased to 281 ± 10 MPa at 1800°C in a high-purity flowing argon atmosphere. The flexure strength of ZW5 was 512 ± 40 MPa at room temperature, and had no degradation even up to 1800°C. The fine and homogeneous microstructure of ZW5 and the removal of oxygen impurity from the grain boundaries promoted the enhancement of high-temperature mechanical properties.     

High-performance B4C-LaB6 composite ceramics fabricated via hot-pressing sintering with La2O3 as sintering additive

The B₄C-LaB₆ composite ceramics were fabricated via hot-pressing sintering at 2050 °C and 20 MPa pressure with the mixture of boron carbide (B₄C) and 2–5 wt% lanthanum oxides (La₂O₃) as raw materials. The effects of additive La₂O₃ content on the microstructures and mechanical properties of composite ceramics were investigated, and reaction mechanisms of La₂O₃ and B₄C at different temperatures were studied in detail. La₂CO₅, La₃BO₆ and LaBO₃ were formed by the reactions of La₂O₃ and B₄C at different temperatures, and finally LaB₆ was formed below 1600 °C. The comprehensive mechanical properties of B₄C-LaB₆ composite ceramics were optimized by adding 4 wt% La₂O₃, the flexural strength, fracture toughness and Vickers hardness reached 350 MPa,4.92 MP am^1/2 and 39.08 GPa, respectively. The high densification and flexural strength of composite ceramics achieved in the present study were attributed to LaB₆ hindering the movement of grain boundary. However, the densification was reduced caused by CO as La₂O₃ content increased to 5 wt%. The fast channel was formed via B₄C reacting with La₂O₃, which accelerated migration of B₄C in the sintering process. The content of La₂O₃ played an important role in the fracture mode of the composite ceramics, and ultimately affected the fracture toughness of the composite ceramics.     

Sintering Mechanism and Microstructure of TaC/SiC Composites Consolidated by plasma-activated sintering

TaC/SiC composites with 5 wt% SiC addition were densified by plasma-activated sintering (PAS) at 1500–1800 °C for 5 min under 30 MPa. The effects of plasma-activated sintering on microstructures, densification and mechanical properties of the composites were investigated. The results showed that TaC/SiC composites achieved a relative density more than 99% of the theoretical density at 1600 °C. A low eutectic liquid phase generated by the oxide on the particle surface was observed in the composite to realize a relatively low temperature sintering densification. While the TaC particle size decreased insignificantly with increasing sintering temperature, the transformation of morphology of SiC particles changing from equiaxed to elongated grain was activated, accompanying with a slight particle size decreasing of the SiC phase, thus promoting a relatively high flexural strength of 550 MPa under 1800 °C. Besides, some ultra-fine 2 nm Ta₂Si was observed in the glassy pockets, strengthening the amorphous phase and thus increasing the flexural strength.