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 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.     

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.     

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.     

ZrB2–SiC–G Composite Prepared by Spark Plasma Sintering of In‐Situ Synthesized ZrB2–SiC–C Composite Powders

To avoid introduction of milling media during ball‐milling process and ensure uniform distribution of SiC and graphite in ZrB₂ matrix, ultrafine ZrB₂–SiC–C composite powders were in‐situ synthesized using inorganic–organic hybrid precursors of Zr(OPr)₄, Si(OC₂H₅)₄, H₃BO₃, and excessive C₆H₁₄O₆ as source of zirconium, silicon, boron, and carbon, respectively. To inhabit grain growth, the ZrB₂–SiC–C composite powders were densified by spark plasma sintering (SPS) at 1950°C for 10 min with the heating rate of 100°C/min. The precursor powders were investigated by thermogravimetric analysis–differential scanning calorimetry and Fourier transform infrared spectroscopy. The ceramic powders were analyzed by X‐ray diffraction, X‐ray photoelectron spectroscopy, and scanning electron microscopy. The lamellar substance was found and determined as graphite nanosheet by scanning electron microscopy, Raman spectrum, and X‐ray diffraction. The SiC grains and graphite nanosheets distributed in ZrB₂ matrix uniformly and the grain sizes of ZrB₂ and SiC were about 5 μm and 2 μm, respectively. The carbon converted into graphite nanosheets under high temperature during the process of SPS. The presence of graphite nanosheets alters the load‐displacement curves in the fracture process of ZrB₂–SiC–G composite. A novel way was explored to prepare ZrB₂–SiC–G composite by SPS of in‐situ synthesized ZrB₂–SiC–C composite powders.     

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.     

Oxidation of Polymer‐Derived HfSiCNO up to 1600°C

Oxidation behavior of HfSiCNO ceramics for Hf/Si ratio of 0.09 at 1400°C–1600°C in ambient air is reported. Quantitative X‐ray analysis of oxidized powders shows crystalli‐zation of the amorphous phase into tetragonal hafnia, hafnon, and cristobalite (carbides, seen in inert atmosphere heat treatments are absent). Cross‐sectional SEM shows the oxide overgrowth on the particles to contain precipitates of hafnia/hafnon, while the interior of the particles is decorated with nanoscale grains of hafnia in a necklace‐like formation. The oxidation kinetics of these materials, determined both from weight‐change measurements and from direct observation of oxide overgrowth, are shown to be comparable to the oxidation of SiC single crystals. Oxidation of SiC–SiC minicomposites (straight fiber bundles infiltrated with a SiC matrix), coated with thin films of HfSiCNO prepared by dip‐coating was studied. The overgrowth thicknesses for oxidation time of 1000 h at 1600°C are compared for uncoated, SiCN(O)‐coated, and HfSiCNO‐coated minicomposites.     

Ultra‐High‐Temperature Ceramic HfB2‐SiC Coating for Oxidation Protection of SiC‐Coated Carbon/Carbon Composites

To protect the carbon/carbon (C/C) composites from oxidation, an outer ultra‐high‐temperature ceramics (UHTCs) HfB₂‐SiC coating was prepared on SiC‐coated C/C composites by in situ reaction method. The outer HfB₂‐SiC coating consists of HfB₂ and SiC, which are synchronously obtained. During the heat treatment process, the formed fluid silicon melt is responsible for the preparation of the outer HfB₂‐SiC coating. The HfB₂‐SiC/SiC coating could protect the C/C from oxidation for 265 h with only 0.41 × 10^?2 g/cm² weight loss at 1773 K in air. During the oxidation process, SiO₂ glass and HfO₂ are generated. SiO₂ glass has a self‐sealing ability, which can cover the defects in the coating, thus blocking the penetration of oxygen and providing an effective protection for the C/C substrate. In addition, SiO₂ glass can react with the formed HfO₂, thus forming the HfSiO₄ phase. Owing to the “pinning effect” of HfSiO₄ phase, crack deflecting and crack termination are occurred, which will prevent the spread of cracks and effectively improve the oxidation resistance of the coating.     

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.     

High‐temperature tensile strength and fracture behavior of ZrB2‐SiC‐graphite composite

The tensile behavior of ZrB₂‐SiC‐graphite composite was investigated from room temperature to 1800°C. Results showed that tensile strength was 134.18 MPa at room temperature, decreasing to 50.34 MPa at 1800°C. A brittle‐ductile transition temperature (1300°C) of ZrB₂‐SiC‐graphite composite was deduced from experimental results. Furthermore, the effect of temperature on the fracture behavior of ZrB₂‐SiC‐graphite composite was further discussed by microstructure observations, which showed that tensile strength was controlled by the relaxation of thermal residual stress below 1300°C, and was affected by the plastic flow during 1300°C and 1400°C. At higher temperature, the tensile strength was dominated by the changes of microstructures.     

The Solubility Limit of CaO in α‐Alumina at 1600°C

The solubility limit of Ca in 99.99% pure α‐Al₂O₃ (alumina) was measured using a wavelength dispersive spectrometer mounted on a scanning electron microscope. Al₂O₃ samples were equilibrated at a concentration which ensured saturation of the Al₂O₃ grains with Ca, and were quenched in water from 1600°C. The results were compared with those from samples which were furnace cooled from 1600°C. For the quenched samples, the Ca solubility limit was found to be 51 ± 1 ppm, which is significantly larger than the solubility limit for samples which were furnace cooled (26 ± 1 ppm).     

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.     

Cyclic Oxidation of Ternary Layered Ti2AlC at 600–1000°C in Air

The cyclic oxidation of bulk Ti₂AlC at intermediate temperatures of 600–1000°C in air was studied by thermogravimetric analysis. It was demonstrated that Ti₂AlC exhibited good cyclic‐oxidation resistance at temperatures above 700°C. The cyclic‐oxidation kinetics approximately follows a parabolic rate law at 700–1000°C range. The surface scales are dense, resistant to spalling and adhesive to Ti₂AlC substrate. An abnormal oxidation whose cyclic‐oxidation kinetics obeys a linear law is observed at 600°C. As revealed by scanning electron microscope (SEM), oxidation‐induced cracks present at 600°C results in poor protectivity and accounts for the abnormal oxidation. The cracks are caused by the stress associated with the volume expansion due the formation of anatase TiO₂ in the scale.     

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.     

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.     

A Complete Solid Solution with Rutile‐Type Structure in SiO2–GeO2 System at 12 GPa and 1600°C

High pressure and temperature synthesis of compositions made of (Si_1?x,Ge_x)O₂ where x is equal to 0, 0.1, 0.2, 0.5, 0.7, and 1 was performed at 7–12 GPa and 1200–1600°C using a Kawai‐type high‐pressure apparatus. At 12 GPa and 1600°C, all the run products were composed of a single phase with a rutile structure. The lattice constants increase linearly with the germanium content (x), which indicates that the rutile‐type phases in the SiO₂–GeO₂ system form a complete series of solid solutions at these pressure and temperature conditions. Our experimental results show that thermodynamic equilibrium state was achieved in this system at 12 GPa and 1600°C, but not at 1200°C. At lower pressures (7 and 9 GPa) and 1600°C, we observed the decomposition of (Si_0.5,Ge_0.5)O₂ into SiO₂‐rich coesite and GeO₂‐rich rutile phases. The silicon content in the rutile structure increases sharply with pressure in the vicinity of the coesite–stishovite phase transition pressure in SiO₂.     

Volatility diagram of ZrB2‐SiC‐ZrC system and experimental validation

A volatility diagram of zirconium carbide (ZrC) at 1600, 1930, and 2200°C was calculated in this work. Combining it with the existing volatility diagrams of ZrB₂ and SiC, the volatility diagram of a ternary ZrB₂‐SiC‐ZrC (ZSZ) system was constructed in order to interpret the oxidation behavior of ZSZ ceramics. Applying this diagram, the formation of ZrC‐corroded and SiC‐depleted layers and the oxidation sequence of each component in ZSZ during oxidation and ablation could be well understood. Most of the predictions from the diagrams are consistent with the experimental observations on the oxidation scale of dense ZrB₂‐SiC‐ZrC ceramics/coatings after oxidation at 1600°C or ablation at 1930 and 2200°C. The reasons for the discrepancy are also briefly discussed.     

High‐temperature calorimetric study of oxide component dissolution in a CaO–MgO–Al2O3–SiO2 slag at 1450°C

Blast‐furnace slags are formed, as iron ore is reduced to metal, as a molten a mixture of refractory and not easily reducible oxides, largely silica, alumina, lime, and magnesia. Their relatively low silica content makes them basic and poor glass formers. Their thermodynamic properties, though important for modeling their formation and reactivity, as well as furnace heat balance, are poorly known. Solution calorimetry of small amounts of solid oxides in a molten oxide solvent at high temperature (up to about 1500°C) permits direct assessment of energetics of dissolution. The enthalpies of solution of slag forming oxides: CaO, SiO₂, Al₂O₃, MgO, and Fe₂O₃ in a simplified model slag of composition: CaO (45.9 mol%), SiO₂ (35.1 mol%), Al₂O₃ (8.3 mol%), MgO (10.7 mol%) were measured by high‐temperature drop solution calorimetry at 1450°C. For this slag composition, enthalpies of solution become more exothermic in the order: Fe₂O₃ (279.3 ± 20.8 kJ/mol), MgO (56.7 ± 9.1 kJ/mol), Al₂O, (41.6 ± 11.3 kJ/mol), CaO (?4.3 ± 2.3 kJ/mol), and SiO₂, (?20.4 ± 4.4 kJ/mol), reflecting the relatively basic character of this low‐silica melt. Within these fairly large experimental errors, characteristic of calorimetry at this high temperature, there is little or no discernible concentration dependence for these heats of solution. The trends seen for these five solutes parallel those seen for heats of solution of the same oxides in other melts at various temperatures, with changes in magnitude reflecting the differences in acid‐base character of the melts. The new data for quartz show systematic behavior which extends the range of basicity studied for the enthalpy of dissolution of silica. The results provide reliable data for future modeling of the thermal balance of steel‐making furnaces and geologic and ceramic systems.     

Processing of High‐Density Magnesia Spinel Electro‐Conducting Ceramic Composite and its Oxidation at 1400°C

Dense conductive ceramic composites of MgAl₂O₄ and MoSi₂ were processed using combustion synthesis under‐load methodology. The starting reactants were blends of MoO₃, SiO₂, MgO, and Al powders. The study revealed that to obtain dense composite with homogeneous microstructure, 30 wt. % of MoSi₂, 18.5 μm Al average particle size, and 175 MPa load are required. The produced dense composite was found to have a low apparent porosity (<1.0 vol. %), moderate density 4.61 g/cm³, and low electrical resistivity 0.3 Ωcm. The dense composite exhibited excellent thermodynamic stability between its phases at 1400°C in open atmosphere.     

A Comparison of 0°–0° and 45°–45° bridge‐Seeded,YBCO single grains

A variety of multiseeding techniques have been investigated over the past 20 yr in an attempt to enlarge bulk (RE)BCO superconducting samples fabricated by the top‐seeded melt growth (TSMG) process for practical applications. Unfortunately, these studies have failed to establish whether technically useful values of trapped field can be achieved in multiseeded bulk samples. In this work specially designed, 0°–0° and 45°–45° bridge seeds of different lengths have been employed to produce improved alignment of the seeds during the TSMG process. The ability of these bridge‐seeded samples to trap magnetic field, which is the key superconducting property for practical applications of bulk (RE)BCO, is compared for the samples seeded using 0°–0° and 45°–45° bridge seeds of different lengths. The grain boundaries produced by these bridge seeds are analyzed in detail, and the similarities and differences between the two bridge‐seeding processes are discussed.