Oxidation behaviors of (Ti1-xNbx)C ceramic solid solutions

(Ti_1-xNb_x)C (x=0, 0.2, 0.5 and 0.8) ceramic solid solutions were prepared by spark plasma sintering and their oxidation behaviours were investigated at 1000 °C in air. The niobium content was found to exhibit a remarkable influence on the oxidation resistance of (Ti_1-xNb_x)C solid solutions. An optimization of oxidation resistance was achieved in (Ti_0.8Nb_0.2)C. After oxidation at 1000 °C for 4 h, the oxidation layer thickness of (Ti_0.8Nb_0.2)C is less than 1/4 of the oxidation layer thickness of monolithic TiC. The higher oxidation resistance can be ascribed to the presence of Nb-doped rutile TiO₂ phase in the oxidation layer of (Ti_0.8Nb_0.2)C. The (Ti,Nb)O₂ phase suppressed the abnormal grain growth and the formation of cracks in the oxide layer, more importantly, it could effectively sluggish the outward diffusion of titanium during oxidation.     

Compositional effect on mechanical properties of transition-metal carbide solid solutions

Equiatomic multicomponent transition metal carbides containing different metal element numbers and carbide components were prepared from monocarbides by spark plasma sintering. The compositional effect on their mechanical properties were investigated in detail. Results indicate that all solid solutions exhibit higher hardness, strength, and modulus values than those obtained from rule of mixture, and it is prone to obtain higher mechanical properties in high-entropy compositions. Nevertheless, the variations of hardness, strength, toughness, and modulus show diverse trends upon the change of composition in carbide solid solutions. By comparison and analysis, it was concluded that entropy-related solid solution effect is a crucial parameter influencing the mechanical properties of metal carbides, however, other parameters such as microstructure, type of base monocarbides, phase purity are also negligible parameters which can have big influence on the overall mechanical properties.     

Oxidation and self-healing behaviour of spark plasma sintered Ta2AlC

Self-healing and oxidation of spark plasma sintered Ta₂AlC was investigated using a newly developed wedge loaded compact specimen to determine strength recovery in a single specimen. Previous work had predicted dominant Al oxidation leading to dense and strong reaction products to result in favourable healing properties. However, crack-gap filling and strength recovery of Ta₂AlC were not achieved by oxidation at 600 °C. Oxidation below 900 °C in synthetic and atmospheric air resulted in porous Ta-oxides, with no Al₂O₃ formation. DTA up to 1200 °C revealed a two-step reaction process with the final products Ta₂O₅ and TaAlO₄. The study shows that the kinetics may overrule the self-healing MAX-phase design criteria based on thermodynamics.     

Mechanochemically activated synthesis of zirconium carbide nanoparticles at room temperature: A simple route to prepare nanoparticles of transition metal carbides

Mechanically activated syntheses of zirconium carbides (ZrC_x) nanoparticles have been performed via ball milling of Zr powder with toluene. It has been found that the milling time can be used to tune the ratio x of C to Zr. The spark plasma sintering of the ZrC_x nanoparticles has shown that the densification can be achieved at a considerably reduced temperature of 1200 °C. This ball milling procedure has been tried to successfully synthesize the nanoparticles of WC_x, TiC_x, and NbC_x, demonstrating that it is a potential route to prepare the nanoparticles of transition metal carbides.     

Kinetics and evolution of oxide scale during various stages of isothermal oxidation at 1300 °C in spark plasma sintered ZrB2 – SiC – LaB6 composites

The kinetics and oxide scale evolution during isothermal exposure of spark-plasma sintered ZrB₂-20 SiC–LaB₆ (7, 10 or 14 vol%) composites at 1300 °C for 1, 8, or 24 h have been examined. Random mass change observed during the first hour stems from a non-protective scale. The variation of mass gain with time is expressed by near-parabolic rate law during 0−8 h time period, and by relations indicating slower kinetics during 8−24 h, with parabolic rate constants (k_p) decreasing sharply. Microstructural examination has shown a continuously evolving layered oxide scale comprising La₂Si₂O₇, borosilicate glass (BSG), ZrSiO₄, and ZrO₂, where the BSG layer growth rate scales linearly with LaB₆ content during 0−8 h, but shows an opposite trend on further exposure. During both time periods (0−8 and 8−24 h), k_p decreased following a linear relationship with increasing BSG layer thickness, indicating its key role as diffusion barrier for oxygen.     

Post-annealing effect on transparent Mg-Zn aluminate solid solutions fabricated by spark plasma sintering

In MgAl₂O₄ (Mg aluminate) fabricated by pressure sintering, carbon contamination, oxygen vacancy, and other defects exist and cannot be completely removed even after post-annealing. ZnAl₂O₄ (Zn aluminate) has the same crystallographic structure as Mg aluminate and excellent light transmission by post-annealing. In this study, the transmission of (Mg_1-XZn_X)Al₂O₄ spinel, which is a solid solution between Mg aluminate and Zn aluminate, was investigated. After post-annealing, the transmission of (Mg_1-XZn_X)Al₂O₄ spinel was higher than Zn aluminate and Mg aluminate, which means that the absorption center disappeared. Besides, the real in-line transmission is improved by up to 30% by post-annealing, which is related to the driving force to increase the configurational entropy and form a more stable solid solution phase. In solid solution spinel, as the Zn content increases, the optical properties can be improved by post-annealing, but the mechanical properties are slightly decreased.     

Effect of tantalum addition on microstructure and oxidation of spark plasma sintered ZrB2-20vol% SiC composites

Almost full density (>99% theoretical density (ρ_th)) was achieved for ZrB₂-20vol% SiC-Xwt.% Ta (X = 2,5, 5 and 10) composites after Spark Plasma Sintering (SPS) (Temperature: 1900 °C, Pressure: 50 MPa; Time: 3 min). The microstructure of ZrB₂-based composites exhibited core-rim structure and it consists of major crystalline phases (ZrB₂ core, (Zr, Ta)B₂ rim, SiC), minor amounts of ZrO₂ and (Zr, Ta)C solid solution phases. Both the specific weight (from 22.91 to 18.77 mg/cm²) and oxide layer thickness (401–195 μm) of ZrB₂-20vol% SiC composites decreased with increasing addition of Ta after the isothermal oxidation at 1500 °C for 10 h in air. The cross-sectional microstructure of oxidized samples displayed presence of a stack of three distinctive layers, which includes thick dense SiO₂ top layer, SiC depleted intermediate layer and unreacted bulk. The present work clearly demonstrated the advantage of tantalum addition in improving the oxidation resistance of ZrB₂-20vol% SiC.     

Effect of tantalum solid solution additions on the mechanical behavior of ZrB2

Mechanical properties and microstructure were compared for zirconium diboride and two zirconium diboride solid solutions containing 3 and 6 at% tantalum diboride. X-ray diffraction indicated that the ceramics were nearly phase-pure and that tantalum dissolved into the ZrB₂ lattice to form (Zr,Ta)B₂ solid solutions. Microstructural analysis indicated that samples achieved nearly full relative density with average grain sizes that ranged from 3?5 μm. The three compositions had similar values of Young’s modulus (510?531 GPa), shear modulus (225?228 GPa), Vickers hardness (15.2–16.4 GPa), and flexural strength (391?452 MPa). Fracture toughness ranged from 2.6 to 3.7 MPa m^1/2 and with increasing tantalum content, the fracture mode changed from predominantly intergranular to predominantly transgranular. Diboride solid solution materials had comparable properties to the single metal diboride, but differences in microstructure, secondary phases, and strain state among the three ceramics partially obscured the actual effects of the solid solution on fracture behavior.     

Effect of solid solution formation on densification of spark plasma sintered ZrC ceramics with TiC as sintering aid

The densification of ZrC ceramics doped with different contents of TiC prepared by spark plasma sintering at the temperatures between 1750 and 1850°C has been investigated. The microstructure and mechanical properties of the ceramics have been characterised. It was shown that TiC additions effectively promoted the densification process by forming (Zr,Ti)C solid solution. The relative densities and mechanical properties of ZrC samples increased with the increasing of TiC content or the sintering temperature. Ceramic with the content of TiC up to 10 vol.-% sintering at 1850°C showed an excellent combination of properties including a relative density of 98.7%, hardness of 20.8?GPa and flexural strength of 605?MPa.     

Oxidation of TaB2-SiC coatings prepared by spark plasma sintering and effect of pre-oxidation treatments

To suppress the oxidation of TaB₂-SiC coatings, the effects of pre-oxidation temperature on the oxygen hindering properties of TaB₂-SiC coatings were investigated to prepare TaB₂-SiC coatings with enhanced oxidation behavior. The addition of 40 wt% TaB₂ made the oxygen permeability of the coating decrease by 62.16%. However, excessive TaB₂ weakened the oxygen hindering ability of the coating due to the large ion complex ability of Ta⁵⁺. The pre-oxidation temperature at 1500 °C led to a homogeneous dispersion of Ta-oxide nanocrystal particles in the Ta-B-Si-O complex-phase glass layer. In contrast with the untreated samples, the active factor and inert factor values of the TaB₂-SiC coating after pre-oxidation treatment at 1500 °C decreased by 43.12% and 17.33%, respectively, which improved the dynamic stability of the coating during oxidation.     

Low temperature synthesis and spark plasma sintering of a boron carbide with a low residual carbon content

Using spark plasma sintering (SPS), >98.5 % dense boron carbide (B₄C) samples were made from commercially available and lab-synthesised powders made via a low temperature synthesis (LTS) process. The work showed that the LTS powder can be produced in batches of tens to hundreds of grams whilst maintaining a high purity material with lower levels of residual free carbon (20.6–21.3 wt.% C) than commercially available samples (22.4 wt.% C). The LTS material was seen to exhibit higher hardness values (37.8 GPa) than the commercial grade material (32.5 GPa) despite featuring a coarser average grain size (10.8 μm and 2.4 μm respectively). This is largely thought to be due to the influence of ZrO₂ and AlB₂ impurities introduced to the material during micronising milling of the powder after synthesis, as opposed to the influence of the materials lower carbon content.     

Pursuing enhanced oxidation resistance of ZrB2 ceramics by SiC and WC co-doping

The oxidative degradation of ZrB₂ ceramics is the main challenge for its extensive application under high temperature condition. Here, we report an effective method for co-doping suitable compounds into ZrB₂ in order to significantly improve its anti-oxidation performance. The incorporation of SiC and WC into ZrB₂ matrix is achieved using spark plasma sintering (SPS) at 1800?°C. The oxidation behavior of ZrB₂-based ceramics is investigated in the temperature range of 1000?°C–1600?°C. The oxidation resistance of single SiC-doped ZrB₂ ceramics is improved due to the formation of silica layer on the surface of the ceramics. As for the WC-doped ZrB₂, a dense ZrO₂ layer is formed which enhances the oxidation resistance. Notably, the SiC and WC co-doped ZrB₂ ceramics with relative density of almost 100% exhibit the lowest oxidation weight gain in the process of oxidation treatment. Consequently, the co-doped ZrB₂ ceramics have the highest oxidation resistance among all the samples.     

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.     

Synthesis of Hf6Ta2O17 superstructure via spark plasma sintering for improved oxidation resistance of multi-component ultra-high temperature ceramics

Ultra-high temperature ceramics (UHTCs) have shown aspiration to overcome challenges in the thermal protection system (TPS) by designing new materials referred to as multi-component UHTCs (MC-UHTCs) in the compositional space. MC-UHTCs have shown remarkable improvement in oxidation resistance due to the formation of the Hf₆Ta₂O₁₇ superstructure during plasma exposure. Herein, the Hf₆Ta₂O₁₇ superstructure is synthesized via a solid-state reaction between HfO₂ and Ta₂O₅ powder mixtures during spark plasma sintering (SPS). The compositions chosen are 50 vol% of HfO₂ -50 vol% of Ta₂O₅ (50HO-50TO) and 70 vol% of HfO₂ -30 vol% of Ta₂O₅ (70HO-30TO). The phase quantification via Rietveld analysis showed Hf₆Ta₂O₁₇ as a principal phase with some residual Ta₂O₅ phase in both the samples. The high-temperature thermal stability of the samples was evaluated using high-velocity plasma jet exposure for up to 3 min. 50HO-50TO was able to withstand the intense plasma condition, which is attributed to the higher content of the Hf₆Ta₂O₁₇ phase (～84%) and lower strain in the Ta₂O₅ phase. The augmentation in the Hf₆Ta₂O₁₇ phase to 94.7% (in 50HO-50TO) post plasma exposure has been attributed to the invariant transformation from a liquid state to Hf₆Ta₂O₁₇ at temperatures >2500 °C during testing. The mechanical integrity is elucidated from the insignificant change in the hardness ～13.3 GPa before and 11.2 GPa after plasma exposure of the 50HO-50TO sample. As a result, the Hf₆Ta₂O₁₇ superstructure's thermo-mechanical stability suggests developing novel oxidation-resistant MC-UHTCs in compositional space for reusable space vehicle applications.     

Predicting oxidation damage of ultra high-temperature carbide ceramics in extreme environments using machine learning

Determining the oxidation resistance of UHTC carbides in extreme environments is challenging theoretically and experimentally due to the high dimensional complexity of influencing variables and intricate testing setups. Herein we demonstrate the use of machine learning (ML) models trained with experimental literature data to predict the oxide thickness of UHTC carbides exposed to air based on composition, mean grain size, relative densification, holding time, and temperature. A multi-dimensional database with 76 occurrences is created containing experimental results of Hf, Zr, and Ta carbides plus additives. The preprocessed database is then used to train ML models to predict their oxidation behavior. The trained model predicts the oxidation damage in the form of an average oxide thickness in UHTC carbides with a Mean Absolute Error (MAE) of ±65.45 μm for samples in the testing set that developed thicknesses up to 1000 μm. The model successfully predicted oxidation damage for a recession rate lower than 60 μm/min. It is noticed that the ensemble method MAE is increased to ±134.34 μm while forecasting the oxidation of samples with a recession rate higher than the threshold. The unprecedented approach is a novel way to predict the damage through the oxidation of carbide compounds before processing for a smarter design with room for improvement.     

Effects of Si3N4 and WC on the oxidation resistance of ZrB2/SiC ceramic tool materials

ZrB₂/SiC, ZrB₂/SiC/Si₃N₄ and ZrB₂/SiC/WC ceramic tool materials were prepared by spark plasma sintering technology, and their oxidation resistance was tested at different oxidation temperatures. When the oxidation temperature is 1300 °C, the oxide layer thickness, oxidation weight gain and flexural strength of ZrB₂/SiC/Si₃N₄ ceramic tool material after oxidation are 8.476 μm, 1.436 mg cm^?2 and 891.0 MPa, respectively. Compared with ZrB₂/SiC ceramic tool materials, the oxide layer thickness and oxidation weight gain are reduced by 8.2% and 11.8%, respectively, and the flexural strength after oxidation is increased by 116.1%. However, the addition of WC significantly reduces the oxidation resistance of the ceramic tool material. A dense oxide film is formed on the surface of ZrB₂/SiC/Si₃N₄ ceramic tool material during oxidation, which effectively prevents oxygen from entering the inside of the material, thereby improving the oxidation resistance of the ceramic tool material.     

Reaction synthesis of spark plasma sintered MoSi2-B4C coatings for oxidation protection of Nb alloy

MoSi₂-B₄C coatings with different B₄C contents were prepared on Nb alloy by spark plasma sintering (SPS) process. Powder mixtures of Mo, Si and B₄C were used as the coating starting materials. Besides MoSi₂ and B₄C phases, small amounts of SiC and MoB are also found in the coatings because of the reactions of Mo, Si and B₄C powders during sintering. Compared with single MoSi₂ coating, the MoSi₂-B₄C coatings show better oxidation resistance at 1450?℃, and dense B₂O₃-SiO₂ oxide scales form after 100?h oxidation. The B₄C or MoB in the MoSi₂-B₄C coatings can serve as the B donor for the formation of B₂O₃. A slight degradation in the microstructure of the MoSi₂-B₄C coatings after oxidation is observed, which can be attributed to the presence of an NbB layer in the inter-diffusion zone of the coatings that retards the inward diffusion of Si from the coating into the substrate alloy. The microstructure development and oxidation behavior of the MoSi₂-B₄C coatings have been discussed.     

Oxidation of ultrahigh temperature ceramics: kinetics,mechanisms, and applications

Materials capable of oxidizing in a protective manner at ultrahigh (>1700 °C) temperatures are needed to push beyond this barrier defined by SiC. Although possessing attractive mechanical properties and oxidation resistance, SiC-based materials are ultimately temperature limited by the melting point of SiO₂. The vast array of ultra-high and high temperature ceramic literature indicates the majority of these materials, like borides, carbides, MAX-phases, and high-entropy ceramics, fall woefully short regarding oxidation resistance. However, for specific applications, like low-orbit aeropropulsion, high ballistics coefficient atmospheric re-entry, and hypersonic cruise, there are a few promising materials. In the present review, oxidation criteria are gathered to build application specific heuristics and are then applied to a multitude of ultra-high temperature ceramics to gauge material efficacy. Discussion of oxidation kinetics, mechanisms and reaction products is offered for each material, identifying strengths, weaknesses, and the remaining gaps in our knowledge.     

Solid solution synthesis of tantalum carbide‐hafnium carbide by spark plasma sintering

Solid solutions of Tantalum carbide (TaC) and Hafnium carbide (HfC) were synthesized by spark plasma sintering. Five different compositions (pure HfC, HfC‐20 vol% TaC, HfC‐ 50 vol% TaC, HfC‐ 80 vol% TaC, and pure TaC) were sintered at 1850°C, 60 MPa pressure and a holding time of 10 min without any sintering aids. Near‐full density was achieved for all samples, especially in the HfC‐contained samples. The porosity in pure TaC samples was caused by the oxygen contamination (Ta₂O₅) on the starting powder surface. The addition of HfC increased the overall densification by transferring the oxygen contamination from TaC surface and forming ultrafine HfO₂ and Hf‐O‐C grains. With the increasing HfC concentration, the overall grain size was reduced by 50% from HfC‐ 80 vol% TaC to HfC‐20 vol% TaC sample. The solid solution formation required extra energy, which restricted the grain growth. The lattice parameters for the solid solution samples were obtained using X‐ray diffraction which had an excellent match with the theoretical values computed using Vegard's Law. The mechanical properties of the solid solution samples outperformed the pure TaC and HfC carbides samples due to the increased densification and smaller grain size.     

Microstructure and mechanical properties of multiwalled carbon nanotube toughened spark plasma sintered ZrB2 composites

ZrB₂ based composites containing 10 vol.-% carbon nanotubes (CNTs) are synthesised by spark plasma sintering at temperatures ranging from 1600 to 18008C and at an applied pressure of 25?MPa. The effects of sintering temperature on densification behaviour, microstructural evolutions and mechanical properties are presented. Results indicate that ZrB₂-CNT composites fabricated at 16508C have the optimal combination of dense microstructure and properties. The fracture toughness is sensitive to the temperature change and reaches 7.2?MPa m^1/2 for the CNT toughened ZrB₂ ceramics, which is higher than the measured result for monolithic ZrB₂ (3.3?MPa m^1/2). The crack deflection and CNT pullout are the dominant toughening mechanisms.