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.     

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.     

Elevated Temperature Strength Enhancement of ZrB2–30 vol% SiC Ceramics by Postsintering Thermal Annealing

The mechanical properties of dense, hot‐pressed ZrB₂–30 vol% SiC ceramics were characterized from room temperature up to 1600°C in air. Specimens were tested as hot‐pressed or after hot‐pressing followed by heat treatment at 1400°C, 1500°C, 1600°C, or 1800°C for 10 h. Annealing at 1400°C resulted in the largest increases in flexure strengths at the highest test temperatures, with strengths of 470 MPa at 1400°C, 385 MPa at 1500°C, and 425 MPa at 1600°C, corresponding to increases of 7%, 8%, and 12% compared to as hot‐pressed ZrB₂–SiC tested at the same temperatures. Thermal treatment at 1500°C resulted in the largest increase in elastic modulus, with values of 270 GPa at 1400°C, 240 GPa at 1500°C, and 120 GPa at 1600°C, which were increases of 6%, 12%, and 18% compared to as hot‐pressed ZrB₂–SiC. Neither ZrB₂ grain size nor SiC cluster size changed for these heat‐treatment temperatures. Microstructural analysis suggested additional phases may have formed during heat treatment and/or dislocation density may have changed. This study demonstrated that thermal annealing may be a useful method for improving the elevated temperature mechanical properties of ZrB₂‐based ceramics.     

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.     

Oxygen diffusion mechanisms during high‐temperature oxidation of ZrB2‐SiC

Oxygen diffusion mechanisms during oxidation of ZrB₂‐30 vol% SiC were explored at temperatures of 1500°C and 1650°C using an ¹⁸O tracer technique. Double oxidation experiments in ¹⁶O₂ and ¹⁸O₂ were performed using a modified resistive heating system. A combination of scanning electron microscopy, energy‐dispersive spectroscopy, and time‐of‐flight secondary ion mass spectrometry was used to characterize the borosilicate and ZrO₂ oxidation products. Oxygen exchange with the borosilicate network was observed to occur quickly at the oxygen‐borosilicate surface at both 1500°C and 1650°C, while evidence of oxygen permeation was only observed at 1650°C for short time (<1 min) exposures. At longer times, >5‐9 min, complete oxygen exchange throughout both the borosilicate glass and ZrO₂ was observed at both temperatures preventing identification of the oxygen transport mechanisms, but demonstrating that oxygen transport is rapid in both oxide phases.     

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.     

High-temperature bending strength,internal friction and stiffness of ZrB2–20 vol% SiC ceramics

Dense ZrB₂–20 vol% SiC ceramics (ZS) were fabricated by hot pressing using self-synthesized high purity ZrB₂ and commercial SiC powders as raw materials. The high temperature flexural strength of ZS and its degradation mechanisms up to 1600 °C in high purity argon were investigated. According to the fracture mode, crack origin and internal friction curve of ZS ceramics, its strength degradation above 1000 °C is considered to result from a combination of phenomena such as grain boundary softening, grain sliding and the formation of cavitations and cracks around the SiC grains on the tensile side of the specimens. The ZS material at 1600 °C remains 84% of its strength at room temperature, which is obviously higher than the values reported in literature. The benefit is mainly derived from the high purity of the ZrB₂ powders.     

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.     

Pressureless sintering of Al2O3 containing up to 20 vol% zirconium diboride (ZrB2)

The production of particle composites by means of pressureless sintering provides a cost-effective alternative to production variants such as hot-pressing. However, minimal quantities of additives are sufficient to impede the densification of oxidic matrix components. This paper examines the sintering behaviour of alumina powder as a function of the volume fraction of ZrB₂ (up to 20 vol%). A distinction can be made between two sintering ranges according to the temperature: at T⩽1700° a solid-state process applies. This process is decisively influenced by the boron oxide (B₂O₃) contained in the raw material ZrB₂. The validity of the Lange model, which describes the influence of increasing volumes of inclusions on the densification behaviour of a crystalline matrix phase, is confirmed in this temperature range. At T>1700°C, an aluminium borate melt occurs, accelerating the sintering process substantially. As a result, the composites quickly attain matrix densities greater than 95% of the theoretical density. At higher firing temperatures the ZrB₂ particles coalesce, resulting in the formation of an electrically conductive penetration structure at a content level of 20 vol%.     

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.     

Oxidation Behavior of ZrB2–SiC Composites at Low Pressures

ZrB₂‐60 mol%SiC composite with a eutectic microstructure was oxidized at 1573 to 1873 K with reduced total pressures (P_tot) and low oxygen partial pressures (). The mass change was continuously measured by a thermobalance, and then fit with a multiple paralinear model. Oxidation scale of SiO₂/ZrO₂+SiO₂/ZrO₂/ZrB₂ was formed at  > 0.13 kPa, whereas only porous ZrO₂ remained at  < 0.13 kPa, P_tot < 1.33 kPa and higher than 1773 K. With increasing , the parabolic oxidation constant decreased, whereas the linear oxidation constant increased.     

High‐temperature mechanical behavior of ZrB2‐based composites with micrometer‐ and nano‐sized SiC particles

Using micrometer‐ and nano‐sized SiC particles as reinforcement phase, two ZrB₂‐SiC composites with high strength up to 1600°C were prepared using high‐energy ball milling, followed by hot pressing. The composite microstructure comprised finer equiaxed ZrB₂ and SiC grains and intergranular amorphous phase. The temperature dependency of flexure strength related to the initial particle size of SiC. In the case of micrometer‐sized SiC, the high‐temperature strength was improved up to 1500°C compared to room‐temperature strength, but the strength degraded at 1600°C, with strength values of 600‐770 MPa. In the case of nano‐sized SiC, the enhanced high‐temperature strength was observed up to 1600°C, with strength values of 680‐840 MPa.     

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.     

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.     

凝胶成型Al2O3-(30vol%)MgO·1.35Al2O3泡沫陶瓷的研制

以板状刚玉和富铝尖晶石为主原料,采用泡沫浸浆凝胶工艺制备了Al2O3-(30 vol%)MgO@1.35Al2O3泡沫陶瓷.研究了分散剂AN-2000与pH值对Al2O3-(30vol%)MgO@1.35Al2O3混合浆料流变特性的影响.在pH值=9.5、AN-2000添加量为0.4 mL@m-2的条件下制备的粘度为O.14 Pa@s,固相体积分数为55%的Al2O3-(30vol%)MgO@1.35Al2O3混合浆料,通过有机泡沫浸浆、引发凝胶反应、湿坯干燥、排胶和烧结,制备出了气孔率为89.3%,强度为5.2 MPa的Al2O3-(30vol%)MgO@1.35Al2O3泡沫陶瓷.     

Hierarchical growth of BiOCl on SrO‐Bi2O3‐B2O3 glass‐ceramics for self‐cleaning applications

We have grown hierarchical structure of bismuth oxycloride (BiOCl) on SrO‐Bi₂O₃‐B₂O₃ (SBBO) transparent glass‐ceramic. SBBO glass‐ceramics were fabricated via conventional melt‐quenching technique while BiOCl was grown by etching the glass via HCl. Enhanced visible light driven photocatalytic activity and increasing hydrophobic feature were observed on BiOCl grown SBBO than as‐quenched SBBO glass‐ceramics. Contact angle analysis showed maximum contact angle of 130.7° on the surface of most BiOCl grown SBBO glass‐ceramic. Furthermore, under visible light illumination water contact angle decreased from 130.7° to 30.8°. Such photo‐induced hydrophilicity and catalytic performance in translucent glass‐ceramics lead self‐cleaning applications.     

Evaluation of Rare‐Earth Modified ZrB2–SiC Ablation Resistance Using an Oxyacetylene Torch

Rare‐earth modified ZrB₂–SiC coatings were prepared via mechanical mixing Sm₂O₃ or Tm₂O₃ powders with spray‐dried ZrB₂, or by chemically doping samarium ions into spray‐dried ZrB₂. In either approach, SiC powders were also added and coatings were fabricated via shrouded air plasma spray. An oxyacetylene torch was utilized to evaluate the coatings under high heat flux conditions for hold times of 30 and 60 s. The resulting phases and microstructures were evaluated as a function of rare‐earth type, modification approach, and ablation time. A brittle m‐ZrO₂ scale was observed in the ZrB₂/SiC‐only coating after ablative tests; during cooling this scale detached from the unreacted coating. In contrast, rare‐earth modified coatings formed a protective oxide scale consisting primarily of either Sm_0.2Zr_0.8O_1.9 or Tm_0.2Zr_0.8O_1.9, along with small amount of m‐ZrO₂. These rare‐earth oxide scales displayed high thermal stability and remained adhered to the unreacted coating during heating and cooling, offering additional oxidation protection.     

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.     

Druck‐ und Bruchverhalten von γ‐Al2O3‐Granulaten

The material behaviour of dominant elastic‐plastic, spherical γ‐Al₂O₃‐granules at compression until primary breakage has been experimentally studied. The influence of particle size and moisture content on the compression behaviour was also investigated. The mechanical properties of the granules can be determined using the recorded force‐displacement curves. Additionally, the specific fracture energy distribution and the distribution of the equivalent impact velocity at fracture can be derived from the force‐displacement curves.     

Infrared radiative performance and anti-ablation behaviour of Sm2O3 modified ZrB2/SiC coatings

To improve the emissivity of ZrB₂/SiC coatings for serving in more serious environment, ZrB₂/SiC coatings with varying contents of high emissivity Sm₂O₃ were fabricated using atmospheric plasma spraying. The microstructure, infrared radiative performance and anti-ablation behaviour of the modified coatings were investigated. The results showed that as the content of Sm₂O₃ increased, the density of the coatings increased because of the low melting point of Sm₂O₃. When the content of Sm₂O₃ was 10 vol%, the coating had the highest emissivity in the 2.5–5 μm band at 1000 °C, up to 0.85, because of the oxygen vacancies promoting additional electronic transitions. Due to the high emissivity, the surface temperature of the coating modified with 10 vol% Sm₂O₃ decreased by 300 °C, which led to little volatilisation of the sealing phase. Further, the mass ablation ratio of the above coating was 3.19 × 10^?4 g/s, decreasing 31% compared to that of a ZrB₂/SiC coating. The formed dense surface structure of the coatings showed considerable oxygen obstructive effects. These findings indicate that the modified coatings show considerable anti-ablation performance, which provides effective anti-ablation protection for the C/C composite substrate.