Effect of AlN Substitutions on the Oxidation Behavior of ZrB2–SiC Composites at 1600°C

The oxidation behavior of ZrB₂–SiC composites, with varying amounts of AlN substituting for ZrB₂, was studied isothermally under static ambient air at 1600°C for up to 5 h. Small amounts of AlN substitutions (≤10 vol%) were found to result in marginal improvement in the oxidation resistance, whereas larger amounts resulted in a significant deterioration. The size of ZrO₂ clusters formed on the oxidized surface was found to be a function of the AlN content. This effect was more pronounced after longer oxidation times (~1 h) as opposed to shorter durations (~5 min). It was postulated that presence of AlN results in the formation of Al₂O₃ during the oxidation process, subsequently resulting in a lowering of viscosity of the glassy silica scale, which facilitates the coarsening of ZrO₂ clusters. This also increases oxygen permeation through the scale which adversely affects the oxidation resistance of the high AlN content composites.     

Oxidation Behavior of Hot Pressed ZrB2‐ZrC‐SiC Ceramic Composites

Dense ZrB₂‐SiC ceramics containing 40 vol% ZrC particles are fabricated via hot pressing method. Then the sintered ceramics are oxidized in air up to 1500°C, and the oxidation kinetics of the ceramic composites is deduced in combination with the reacted fraction curves. As indicated by the experimental results, the oxidation kinetics changes from reaction‐controlled process to diffusion‐controlled one with increasing of oxidation temperature. In addition, the oxidation kinetics parameters are obtained, which indicates that the oxidation resistance decays at elevated temperatures. Furthermore, the evolution of surface morphology and oxide scale during oxidation process is clarified.     

Mechanical Characterization of Annealed ZrB2–SiC Composites

Composites consisting of 70 vol% ZrB₂ and 30 vol% α‐SiC particles were hot pressed to near full density and subsequently annealed at temperatures ranging from 1000°C to 2000°C. Strength, elastic modulus, and hardness were measured for as‐processed and annealed composites. Raman spectroscopy was employed to measure the thermal residual stresses within the silicon carbide (SiC) phase of the composites. Elastic modulus and hardness were unaffected by annealing conditions. Strength was not affected by annealing at 1400°C or above; however, strength increased for samples annealed below 1400°C. Annealing under uniaxial pressure was found to be more effective than annealing without applied pressure. The average strength of materials annealed at 1400°C or above was ~700 MPa, whereas that of materials annealed at 1000°C, under a 100 MPa applied pressure, averaged ~910 MPa. Raman stress measurements revealed that the distribution of stresses in the composites was altered for samples annealed below 1400°C resulting in increased strength.     

TEM Study of the High‐Temperature Oxidation Behavior of Hot‐Pressed ZrB2–SiC Composites

The oxidation behaviors of ZrB₂‐ 30 vol% SiC composites were investigated at 1500°C in air and under reducing conditions with oxygen partial pressures of 10⁴ and 10 ^{? 8} Pa, respectively. The oxidation of ZrB₂ and SiC were analyzed using transmission electron microscopy (TEM). Due to kinetic difference of oxidation behavior, the three layers (surface silica‐rich layer, oxide layer, and unreacted layer) were observed over a wide area of specimen in air, while the two layers (oxide layer, and unreacted layer) were observed over a narrow area in specimen under reducing condition. In oxide layer, the ZrB₂ was oxidized to ZrO₂ accompanied by division into small grains and the shape was also changed from faceted to round. This layer also consisted of amorphous SiO₂ with residual SiC and found dispersed in TEM. Based on TEM analysis of ZrB₂ – SiC composites tested under air and low oxygen partial pressure, the ZrB₂ begins to oxidize preferentially and the SiC remained without any changes at the interface between oxidized layer and unreacted layer.     

Oxidation of ZrB2–SiC‐Graphite Composites Under Low Oxygen Partial Pressures of 500 and 1500 Pa at 1800°C

The oxidation behavior of ZrB₂–SiC‐graphite composites under low oxygen partial pressures of 500 and 1500 Pa at 1800°C was investigated. The phase composition and microstructure of the oxidized scale were characterized using TEM, SEM, XRD, XPS, EDS. The analytical results indicated that a low oxygen partial pressure had a remarkable effect on the oxidation mechanism of ZrB₂–SiC‐graphite composites. When oxidized at 1500 Pa, the oxidation kinetics was controlled by the rate of oxygen diffusion into the composite. When the composite was oxidized at 500 Pa, control of the oxidation kinetics changed from the rate of oxygen diffusion to the rate of the oxidation reaction. The rate of oxidation decreased with decreasing oxygen partial pressure. Higher partial pressures of oxygen resulted in less oxidation resistance by the ZrB₂–SiC‐graphite composites.     

Initial Stages of ZrB2–30 vol% SiC Oxidation at 1500°C

The initial oxidation behavior of ZrB₂–30 vol% SiC was analyzed with the goal of understanding any relationship to the variable oxidation performance observed at longer times. A box furnace was used to oxidize samples for times as short as 10 s and up to 100 min at 1500°C in air. The samples were characterized using mass change, scanning electron microscopy, energy dispersive spectroscopy, X‐ray diffraction, and X‐ray photoelectron spectroscopy to explore the oxidation behavior. The presence of borosilicate glass and ZrO₂ was observed on the surface at times as early as 10 s. Bubble formation in the borosilicate glass was observed after 30 s of oxidation and is attributed to uneven distribution of the glass. The impact of surface roughness on oxidation was also explored and found to be negligible for times greater than 30 s.     

SiC Depletion in ZrB2–30 vol% SiC at Ultrahigh Temperatures

The formation of a porous SiC‐depleted region in ZrB₂–SiC due to active oxidation at ultrahigh temperatures was characterized. The presence/absence of SiC depletion was determined at a series of temperatures (1300°C–1800°C) and times (5 min–100 h). At T < 1627°C, SiC depletion was not observed. Instead, the formation of a ZrO₂ + C/borosilicate oxidation product layer sequence was observed above the ZrB₂–SiC base material. At T ≥ 1627°C, SiC was depleted in the ZrB₂ matrix below the ZrO₂ and borosilicate oxidation products. The SiC depletion was attributed to active oxidation of SiC to form SiO(g). The transition between C formation in ZrO₂ (T < 1627°C) and SiC depletion in ZrB₂ (T ≥ 1627°C) is attributed to variation in the temperature dependence of thermodynamically favored product assemblage influenced by the local microstructural phase distribution. The growth kinetics of the SiC depletion region is consistent with a gas‐phase diffusion‐controlled process.     

High‐Temperature Oxidation of ZrB2–SiC–AlN Composites at 1600°C

The effect of AlN substitution on oxidation of ZrB₂–SiC was evaluated at 1600°C up to 5 h. Replacement of ZrB₂ by AlN, with 30 vol% SiC resulted in improved oxidation resistance with a thinner scale and reduced oxygen affected area. On the other hand, substitution of AlN for SiC resulted in a deterioration of the oxidation resistance with an abnormal scale and significant recession. The effect of SiC content was also studied, and was found to be consistent with the literature for the composites without AlN additions. A similar effect was observed when AlN was added, with the higher SiC content materials showing improved oxidation resistance. X‐ray photoelectron spectroscopy showed the presence of Al₂O₃ and SiO₂ on the surface, which could possibly lead to a modification in the viscosity of the glassy oxide scale. Possibly, the oxidation behavior of ZrB₂–SiC composites can be improved with controlled AlN additions by adjusting the Al:Si ratios.     

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.     

Oxidation Behavior of SiC Whiskers at 600–1400°C in Air

The oxidation behavior of SiC whiskers (SiC_W) with a diameter size of 50–200 nm has been investigated at 600°C–1400°C in air. Experimental results reveal that SiC_W exhibit a low oxidation rate below 1100°C while a significant larger oxidation rate after that. This can be attributed to the small diameter size of SiC_W, which determines that it is hard to form a protective SiO₂ layer thick enough to hamper the diffusion of oxygen effectively. Both nonisothermal and isothermal oxidation kinetics were studied and the apparent oxidation energy was calculated to further understand the oxidation behavior of the SiC_W.     

Mechanisms for Variability of ZrB2‐30 vol% SiC Oxidation Kinetics

The oxidation kinetics of ZrB₂‐30 vol% SiC were analyzed statistically with the goal of understanding the underlying mechanisms for observed variability. A box furnace was used to oxidize specimens for times between 30 s and 100 h at temperatures of 1300°C–1550°C in air. The specimens were characterized to determine weight change, scale thickness, and scale composition to quantify the oxidation behavior. Weight gain measurements of different specimens after 100 min of exposure showed differences of up to 2 mg/cm² for the same testing conditions where the average weight gain was 2.54 mg/cm². Variation of 30%–80% was observed in the average thickness of each layer of the oxide within a single specimen. Viscous glass flow was ruled out as a potential mechanism. Glass bubble formation was proposed as the main cause for oxidation kinetics variability.     

ZrB2-SiC/C层状复合陶瓷的高温氧化行为

利用流延法成膜和热压烧结工艺制备出了ZrB2-SiC层和石墨层交替排列、层厚均匀、界面清晰的ZrB2-SiC/C层状复合陶瓷.采用循环氧化法对ZrB2-SiC和ZrB2-SiC/C层状复合陶瓷在1000℃及1300℃空气中的氧化动力学曲线进行了研究.结果表明:在1000℃氧化增重时,ZrB2-SiC/C层状复合陶瓷在氧化反应初期表现为氧化增重,随着时间的增加,表现为氧化减重.在1300℃时,ZrB2-SiC/C层状复合陶瓷由于基体层ZrB2-SiC和弱夹层石墨相的氧化规律的相互叠加,使得其氧化增重曲线表现为抛物线规律.由XRD分析及扫描电镜观察发现,1300℃氧化15 h后,试样中不存在弱夹层石墨相,由于石墨相的挥发,材料残留孔隙.     

ZrB2–ZrCxN1−x Eutectic Composites Produced by Melt Solidification

Ceramic eutectics are naturally occurring in‐situ composites and can offer superior mechanical properties. Here, ZrB₂–ZrC_xN_1?x quasi‐binary ceramic eutectic composites were produced by arc‐melting a mixture of ZrB₂, ZrC, and ZrN powders in an N₂ atmosphere. The arc‐melted ZrB₂–ZrC_xN_1?x composites containing 50 mol% of ZrB₂ (irrespective of the ZrC/ZrN ratio) showed rod‐like eutectic structures, where ZrC_xN_1?x single‐crystalline rods were dispersed in the ZrB₂ single‐crystalline matrices. Multiple orientation relationships between the ZrC_xN_1?x rods and the ZrB₂ matrices were observed, and one was determined as ZrB₂ {} //Zr_xN_1?x {111} and ZrB₂ < > //ZrC_xN_1?x < > . The rod‐like eutectic composites had higher hardness than the hypo‐ and hypereutectic composites and the 50ZrB₂–40ZrC–10ZrN (mol%) eutectic composite showed the highest Vickers hardness (H_v) of 19 GPa.     

Dynamic Compressive Behavior of ZrB2‐Based Ceramic Composites at Room Temperature and 1073 K

The dynamic compressive behaviors of ZrB₂‐based ceramic composites were investigated through the convenient and high‐temperature Splitting Hopkinson Pressure Bars. The effects of strain rate on dynamic compressive strength, stress–strain relationship and fracture mechanisms were discussed in detail. Moreover, the influence of pre‐oxidation on dynamic strength was also studied at 1073 K. The results indicate that the relationship between dynamic compressive stress and strain for ZrB₂‐SiC‐graphite composite is strong nonlinear at room temperature and 1073 K. Dynamic compressive strength increases linearly with the increase of strain rate. The pre‐oxidation effect results in the enhancement of dynamic compressive strength at 1073 K in comparison with the room temperature strength. Based on the microstructures, the dominant intergranular fracture and pull‐out of graphite flake are observed at low strain rates, whereas the transgranular fracture and cutting of graphite flake are found at high strain rates. Fracture mechanisms play a crucial role on the changes of dynamic compressive strength and critical strain with strain rate.     

Thermal Shock Resistance of Laminated ZrB2–SiC Ceramic Evaluated by Indentation Technique

In this work, the thermal shock behavior of laminated ZrB₂–SiC ceramic has been evaluated using indentation‐quench method based on propagation of Vickers cracks and compared with the monolithic ZrB₂–SiC ceramic. The results showed that the laminated ZrB₂–SiC ceramic exhibited better resistance to crack propagation and thermal shock under water quenching condition, and the critical temperature difference (ΔT_c) of laminated ZrB₂–SiC ceramic (ΔT_c ≈ 590°C) was much higher than that of monolithic ceramic (ΔT_c ≈ 290°C). The significant improvement in thermal shock resistance was attributed to residual stresses enhancing the resistance to crack growth during thermal shock loading.     

Oxidation of ZrB2 Nanoparticles at High Temperature under Low Oxygen Pressure

The oxidation of ZrB₂ nanoparticles was observed at high temperature of 1500°C under low oxygen partial pressure of 5 × 10^?2 Pa by an environmental transmission electron microscope. The results demonstrate that the oxidation starts on the surface of ZrB₂ nanoparticles with decomposition of ZrB₂ into ZrO₂ and B₂O₃. The nucleation and growth of ZrO₂ on the surface of ZrB₂ proceed with B₂O₃ being evaporated.     

Reactive Hot‐Pressed Hybrid Ceramic Composites Comprising SiC(SCS‐6)/Ti Composite and ZrB2–ZrC Ceramic

In this study, hybrid composites comprising SiC(SCS‐6)/Ti and ZrB₂–ZrC ceramics were prepared by sandwiching Ti/SiC(SCS‐6)/Ti sheets and Zr + B₄C powder layers, followed by reactive hot pressing at 1300°C. The microstructure of the obtained hybrid composites was characterized by field‐emission scanning electron microscopy, transmission electron microscopy, and energy‐dispersive X‐ray spectroscopy. The results show that after reactive hot pressing, a highly dense matrix was achieved in the hybrid composites. A Ti‐rich zone was observed only in the hybrid composite prepared using a 10‐μm‐thick Ti foil. Interface reaction occurred during sintering and interface reaction layers were formed between the fibers and the matrix, and the phases were identified. In addition, the mechanical behavior of the hybrid composites was evaluated using by testing under four‐point bend testing. The results indicate that the hybrid composites exhibited greater flexural strengths and noncatastrophic fracture behavior. The flexural strength ranged from 440 to 620 MPa, depending on the thickness of the Ti foils and the fiber volume amount.     

Separating Test Artifacts from Material Behavior in the Oxidation Studies of HfB2–SiC at 2000°C and Above

Oxidation characteristics of HfB₂‐15 vol% SiC prepared by field‐assisted sintering was examined at 2000°C by heating it in a zirconia‐resistance furnace and by direct electrical resistance heating of the sample. Limitations of the material and the direct electrical resistance heating apparatus were explored by heating samples multiple times and to temperatures in excess of 2300°C. Oxide scales that developed at 2000°C from both methods were similar in that they consisted of a SiO₂/HfO₂ outer layer, a porous HfO₂ layer, and a HfB₂ layer depleted of SiC. But they differed in scale thicknesses, impurities present, scale morphology/complexity. Possible test artifacts are discussed.     

ZrB2–SiC Nano‐Powder Mixture Prepared Using ZrSi2 and Modified Spark Plasma Sintering

ZrB₂–SiC nano‐powder mixture was synthesized using ZrSi₂ source material and a modified spark plasma sintering apparatus. The particle size of ZrB₂ and SiC was about 80 and 20 nm, respectively. The molecular‐level homogeneity of Zr/Si source and fast heating/cooling rate by SPS caused the formation of homogeneously intermixed nano‐powders. A strong exothermal reaction occurred at around 860°C, which caused strong agglomeration and growth of the synthesized powder mixture. The rapid reaction could be controlled by adding 20 wt% of NaCl, which acted as an inert filler.     

Solidification of welded SiC–ZrB2–ZrC ceramics

A silicon carbide‐based ceramic, containing 50 vol% SiC, 35 vol% ZrB₂, and 15 vol% ZrC was plasma arc welded to produce continuous fusion joints with varying penetration depth. The parent material was preheated to 1450°C and arc welding was successfully implemented for joining of the parent material. A current of 138 A, plasma flow rate of ~1 L/min or ~0.5 L/min, and welding speed of ~8 cm/min were utilized for repeated joining, with full penetration fusion zones along the entire length of the joints. Solidification was determined to occur through the crystallization of β‐SiC (3C), then the simultaneous solidification of SiC and ZrB₂, and lastly through the simultaneous solidification of SiC, ZrB₂, and ZrC through a ternary eutectic reaction. The ternary eutectic composition was determined to be 35.3 ± 2.2 vol% SiC, 39.3 ± 3.8 vol% ZrB₂, and 25.4 ± 3.0 vol% ZrC. A dual fusion zone microstructure was always observed due to convective melt pool mixing. The SiC content at the edge of the fusion zone was 57 vol%, while SiC content at the center of the fusion zone was 42 vol% although the overall SiC content was still nominally 50 vol% throughout the entire fusion zone.