Fabrication and Characterization of ZrB2-Based Ceramic Using Synthesized ZrB2–LaB6 Powder

ZrB₂–LaB₆ powder was obtained by reactive synthesis using ZrO₂, La₂O₃, B₄C, and carbon powders. Then ZrB₂–20 vol% SiC–10 vol% LaB₆ (ZSL) ceramics were prepared from commercially available SiC and the synthesized ZrB₂–LaB₆ powder via hot pressing at 2000°C. The phase composition, microstructure, and mechanical properties were characterized. Results showed that both LaB₆ and SiC were uniformly distributed in the ZrB₂ matrix. The hardness and bending strength of ZSL were 17.06±0.52 GPa and 505.8±17.9 MPa, respectively. Fracture toughness was 5.7±0.39 MPa·m^1/2, which is significantly higher than that reported for ZrB₂–20 vol% SiC ceramics, due to enhanced crack deflection and crack bridging near SiC particles.     

Corrosion of ZrB2 Powder During Wet Processing – Analysis and Control

Corrosion behavior of ZrB₂ powder during wet processing in water or ethyl alcohol was studied both with and without an organic additive. Incorporation of oxygen and pH change did not intensively occur during static aging of aqueous slurries, but corrosion was enhanced when stirring the slurries. The oxygen content of the powder increased rather rapidly with milling time in ethyl alcohol. The molecular weight of polyethylenimine effected the pH change and oxygen content of ZrB₂ powder, after corrosion in water for 18 months. X-ray photoelectron spectroscopy analysis informed that the surface of both the pristine and corroded powders was mainly covered with ZrOH, but a certain amount of Zr–B bonding remained at the powder surface after the wet processing.     

Hydrolysis and Dispersion Properties of Aqueous Y2Si2O7 Suspensions

The dispersion of aqueous γ-Y₂Si₂O₇ suspensions, which contain only one component but have a complex ion environment, was studied by the introduction of two different polymer dispersants, polyethylenimine (PEI) and polyacrylic acid (PAA). The suspension without any dispersant remains stable in the pH range of 9–11.5 because of electrostatic repulsion, while it is flocculated upon stirring due to the readsorption of hydrolyzed ions on the colloid surface. However, suspensions with 1 dwb% PEI exhibit greater stability in the pH range of 4–11.5. The addition of PEI shifts the isoelectric point (IEP) of the suspensions from pH 5.8 to 10.8. Near the IEP (pH_IEP=10.8), the stability of the suspensions with PEI is dominated by the steric effect. When the pH is decreased to acid direction, the stabilization mechanism is changed from steric hindrance to an electrosteric effect little by little. PAA also has the effect of reducing the hydrolysis speed via a "buffer effect" in the basic pH range, but the lack of adsorption between the highly ionized anionic polymer molecules and the negative colloid particle surfaces shows no positive effect on hydrolysis of colloids and on the stabilization of Y₂Si₂O₇ suspensions.     

Effect of Polyethylenimine on Hydrolysis and Dispersion Properties of Aqueous Si3N4 Suspensions

The roles of polyethylenimine (PEI) in the hydrolysis and dispersion properties of aqueous Si₃N₄ suspensions were studied in terms of the hydrolysis, adsorption, electrokinetic, and rheological measurements. It was found that the pH change of the suspensions in the acidic environment could be minimized in the presence of ≥0.5 dwb% PEI. The ammonia and oxygen measurements suggest that this phenomenon is primarily attributed to the buffer mechanism generated by the ionized PEI, instead of the protection mechanism. The constant pH enables the suspensions to retain a better stability with time at acidic pH. The adsorption of PEI on Si₃N₄ is a high-affinity type at highly basic pH, but is a low-affinity type at acidic pH. As the PEI amount increases, the adsorption shifts the isoelectric point (IEP) of Si₃N₄ from pH 5.9 to pH ∼11 until complete coverage is attained. The stability of Si₃N₄ suspensions is found to depend strongly on the saturated adsorption of PEI, which is as a function of the pH and PEI amount. Once the saturated adsorption limit is reached, the excess free PEI molecules become more detrimental to the stability with increased solid loading. The stabilization mechanisms of Si₃N₄ suspensions by PEI were discussed in detail.     

Reaction Processes and Characterization of ZrB2 Powder Prepared by Boro/Carbothermal Reduction of ZrO2 in Vacuum

The present work was concentrated mainly on the reaction processes of boro/carbothermal reduction (BCTR) of ZrO₂ with B₄C and carbon in vacuum, and characterization of morphology and sinterability of the obtained ZrB₂ powder. Combining the thermodynamic calculations, X-ray diffraction results, and the trend of furnace pressure with temperature during synthesis, a detailed explanation of the reaction processes of BCTR was developed. Most of the ZrB₂ particles obtained at 1650°C presented a nearly spherical morphology, whereas those synthesized at 1750°C showed a nearly columnar morphology with an increased size. Compared with the powder synthesized at 1750°C as well as the commercially additive-free powder used in the reported work, the ZrB₂ powder synthesized at 1650°C showed a better sinterability due to its smaller particle size and lower oxygen content.     

Transmission Electron Microscopy Characterization of Hot-Pressed ZrB2 with MoSi2 Additive

Microstructure of the hot-pressed ZrB₂ with MoSi₂ additive was investigated by transmission electron microscopy (TEM). The effect of MoSi₂ addition on the microstructure of the ceramic was assessed. For the pure ZrB₂, the microstructure consisted of the equiaxed ZrB₂ grains and a few elongated ZrB₂ grains. For the ZrB₂ with MoSi₂ additive, the microstructure consisted almost entirely of equiaxed ZrB₂ grains. A few dislocations were present in the ZrB₂ grains. In addition, high-resolution TEM observations showed that the intergranular amorphous phase was absent at two ZrB₂ grain boundaries in the ZrB₂ with MoSi₂ additive.     

Low-Temperature Densification of Zirconium Diboride Ceramics by Reactive Hot Pressing

Zirconium diboride–silicon carbide ceramics with relative densities in excess of 95% were produced by reactive hot pressing (RHP) at temperatures as low as 1650°C. The ZrB₂ matrix was formed by reacting elemental zirconium and boron. Attrition milling of the starting powders produced nanosized (<100 nm) Zr particulates that reacted with B below 600°C. The reaction resulted in the formation of nanoscale ZrB₂ crystallites that could be densified more than 250°C below the temperatures required for conventional ZrB₂ powder. Because of the low-temperature densification, the resulting ZrB₂ grain sizes were as small as 0.5±0.30 μm for specimens densified at 1650°C and 1.5±1.2 μm for specimens densified at 1800°C. Vickers hardness, elastic modulus, and flexure strength of fully dense materials produced by RHP were 27, 510, and 800 MPa, respectively.     

Pressureless Sintering of High-Density ZrB2–SiC Ceramic Composites

Ultra-high-temperature ceramic composites of ZrB₂ 20 wt%SiC were pressureless sintered under an argon atmosphere. The starting ZrB₂ powder was synthesized via the sol–gel method with a small crystallite size and a large specific surface area. Dry-pressed compacts using 4 wt% Mo as a sintering aid can be pressureless sintered to ∼97.7% theoretical density at 2250°C for 2 h. Vickers hardness and fracture toughness of the sintered ceramic composites were 14.82±0.25 GPa and 5.39±0.13 MPa·m^1/2, respectively. In addition to the good sinterability of the ZrB₂ powders, X-ray diffraction and scanning electron microscopy results showed that Mo formed a solid solution with ZrB₂, which was believed to be beneficial for the densification process.     

Dispersion of Zirconium Diboride in an Aqueous, High-Solids Paste

The dispersion of ZrB₂ particles was investigated. In aqueous systems, the surface of ZrB₂ consists of a thin layer of ZrO₂ that controls the surface chemistry and surface charge. Measurements showed that the ZrB₂ had an isoelectric point of pH=4.7 and a maximum ζ potential of −50 mV at pH=9. The addition of a dispersant, either an ionic ammonium polyacrylate or a nonionic alkoxylated polyether, increased the ζ potential of ZrB₂ by as much as 60 mV to −110 mV. Viscosity measurements were used to optimize dispersant concentrations. High-solids loading (∼45 vol.% ZrB₂) aqueous pastes were prepared with two different dispersants. The pastes had viscosities of 40–50 Pa·s which was acceptable for extrusion, and were used to fabricate three-dimensional components from ZrB₂.     

Thermophysical Properties of ZrB2 and ZrB2–SiC Ceramics

Thermophysical properties were investigated for zirconium diboride (ZrB₂) and ZrB₂–30 vol% silicon carbide (SiC) ceramics. Thermal conductivities were calculated from measured thermal diffusivities, heat capacities, and densities. The thermal conductivity of ZrB₂ increased from 56 W (m K)⁻¹ at room temperature to 67 W (m K)⁻¹ at 1675 K, whereas the thermal conductivity of ZrB₂–SiC decreased from 62 to 56 W (m K)⁻¹ over the same temperature range. Electron and phonon contributions to thermal conductivity were determined using electrical resistivity measurements and were used, along with grain size models, to explain the observed trends. The results are compared with previously reported thermal conductivities for ZrB₂ and ZrB₂–SiC.     

Oriented Structure and Crystallography of Directionally Solidified LaB6—ZrB2 Eutectic

Directional solidification of LaB₆—ZrB₂, by use of an electron beam heating technique, yielded oriented ZrB₂ fibers in a LaB₆ matrix. The average diameter of the ZrB₂ fibers was ∼0.2–1.2 µm, with fiber lengths up to 100 µm. Primary platelike LaB₆ dendrites formed upon the solidification of an ingot with a composition of LaB₆—18 wt% ZrB₂. LaB₆ was the first phase to nucleate when eutectic growth occurred, and ZrB₂ showed nonfaceted growth. For the ingot solidified with planar growth the orientation relations of the phases were as follows: growth direction, [001]_LaB6∥[00.1]_ZrB2; interfacial plane, (11.0)_LaB6∥(11.0)_ZrB2.     

Thermal Shock Resistance and Fracture Behavior of ZrB2–Based Fibrous Monolith Ceramics

The thermal shock resistance and fracture behavior of zirconium diboride (ZrB₂)-based fibrous monoliths (FM) were studied. FMs containing cells of ZrB₂–30 vol% SiC with cell boundaries composed of graphite–15 vol% ZrB₂ were hot pressed at 1900°C. The average flexure strength of the FMs was 375 MPa, less than half of the strength of hot-pressed ZrB₂–30 vol% SiC. Flexure specimens failed noncatastrophically and retained 50%–85% of their original strength after the first fracture event. A critical thermal shock temperature (Δ T _c) of 1400°C was measured by water quench thermal shock testing, a 250% improvement over the previously reported Δ T _c values for ZrB₂ and ZrB₂–30 vol% SiC of similar dimensions (4 mm × 3 mm × 45 mm). The flexure strength was maintained with Δ T _c values of 1350°C and below. As Δ T _c increased, the stiffness of the flexure specimen decreased linearly. The lower stiffness and improvement in thermal shock resistance is attributed to crack propagation in the cell boundary and crack deflection around the load-bearing cells. The critical thermal shock was attributed to the fracture of the ZrB₂–30% SiC cell material.     

High-Temperature Chemistry and Oxidation of ZrB2 Ceramics Containing SiC, Si3N4, Ta5Si3, and TaSi2

The effect of Si₃N₄, Ta₅Si₃, and TaSi₂ additions on the oxidation behavior of ZrB₂ was characterized at 1200°–1500°C and compared with both ZrB₂ and ZrB₂/SiC. Significantly improved oxidation resistance of all Si-containing compositions relative to ZrB₂ was a result of the formation of a protective layer of borosilicate glass during exposure to the oxidizing environment. Oxidation resistance of the Si₃N₄-modified ceramics increased with increasing Si₃N₄ content and was further improved by the addition of Cr and Ta diborides. Chromium and tantalum oxides induced phase separation in the borosilicate glass, which lead to an increase in liquidus temperature and viscosity and to a decrease in oxygen diffusivity and of boria evaporation from the glass. All tantalum silicide-containing compositions demonstrated phase separation in the borosilicate glass and higher oxidation resistance than pure ZrB₂, with the effect increasing with temperature. The most oxidation-resistant ceramics contained 15 vol% Ta₅Si₃, 30 vol% TaSi₂, 35 vol% Si₃N₄, or 20 vol% Si₃N₄ with 10 mol% CrB₂. These materials exceeded the oxidation resistance of the ZrB₂/SiC ceramics below 1300°–1400°C. However, the ZrB₂/SiC ceramics showed slightly superior oxidation resistance at 1500°C.     

Preparation of Zirconium Boride Powder

An intermediate reaction in the synthesis of ZrB₂ powder by the reduction of ZrO₂ with B₄C and carbon was confirmed through both thermodynamical calculation and experimental results. Because the intermediate product B₂O₃ was volatile, excess boron should be added to compensate for the boron loss in order to prepare high-purity ZrB₂ powder. The synthesis temperatures of the intermediate reaction and carbothermic reduction were, respectively, about 1400 and 1600°C, obtained by experiments. The influence of processing temperature and time on the purity and the particle size of ZrB₂ powder was also investigated.     

Pressureless Densification of Zirconium Diboride with Boron Carbide Additions

Zirconium diboride (ZrB₂) was densified (>98% relative density) at temperatures as low as 1850°C by pressureless sintering. Sintering was activated by removing oxide impurities (B₂O₃ and ZrO₂) from particle surfaces. Boron oxide had a high vapor pressure and was removed during heating under a mild vacuum (∼150 mTorr). Zirconia was more persistent and had to be removed by chemical reaction. Both WC and B₄C were evaluated as additives to facilitate the removal of ZrO₂. Reactions were proposed based on thermodynamic analysis and then confirmed by X-ray diffraction analysis of reacted powder mixtures. After the preliminary powder studies, densification was studied using either as-received ZrB₂ (surface area ∼1 m²/g) or attrition-milled ZrB₂ (surface area ∼7.5 m²/g) with WC and/or B₄C as a sintering aid. ZrB₂ containing only WC could be sintered to ∼95% relative density in 4 h at 2050°C under vacuum. In contrast, the addition of B₄C allowed for sintering to >98% relative density in 1 h at 1850°C under vacuum.     

Effect of Fe and Cr Addition on the Sintering Behavior of ZrB2 Produced by Self-Propagating High-Temperature Synthesis

An investigation of the sintering behavior of ZrB₂ powder with Fe and Cr (0 to 20 wt%) addition was conducted. It was observed that Fe addition helps to enhance the density of ZrB₂ only up to 10 wt%. Further addition of Fe degrades the sintering by segregation of Fe-rich phases. Formation of a eutectic phase containing a Fe:Zr ratio of 92.57:7.43 was also found in Fe-added samples. The addition of Cr to a ZrB₂ matrix was found to result in swelling of the samples, leading to several cracks.     

Thermal and Electric Properties in Hot-Pressed ZrB2–MoSi2–SiC Composites

The thermal and electrical properties of MoSi₂ and/or SiC-containing ZrB₂-based composites and the effects of MoSi₂ and SiC contents were examined in hot-pressed ZrB₂–MoSi₂–SiC composites. The thermal conductivity and electrical conductivity of the ZrB₂–MoSi₂–SiC composites were measured at room temperature by a nanoflash technique and a current–voltage method, respectively. The results indicate that the thermal and electrical conductivities of ZrB₂–MoSi₂–SiC composites are dependent on the amount of MoSi₂ and SiC. The thermal conductivities observed for all of the compositions were more than 75 W·(m·K)⁻¹. A maximum conductivity of 97.55 W·(m·K)⁻¹ was measured for the 20 vol% MoSi₂-30 vol% SiC-containing ZrB₂ composite. On the other hand, the electrical conductivities observed for all of the compositions were in the range from 4.07 × 10–8.11 × 10 Ω⁻¹·cm⁻¹.     

Wet Milling of Fe/Al/Al2O3 and Fe2O3/Al/Al2O3 Powder Mixtures

Wet milling of Al₂O₃-aluminide alloy (3A) precursor powders in acetone has been investigated by milling Fe/Al/Al₂O₃ and Fe₂O₃/Al/Al₂O₃ powder mixtures. The influence of the milling process on the physical and chemical properties of the milled powders has been studied. Particle refinement and homogenization were found not to play a dominant role, whereas plastic deformation of the metal particles leads to the formation of dislocations and a highly disarranged polycrystalline structure. Although no chemical reactions among the powder components in Fe₂O₃/Al/Al₂O₃ powder mixtures were observed, the formation of a nanocrystalline, ordered intermetallic FeAl phase in Fe/Al/Al₂O₃ powder mixtures caused by mechanical alloying was detected. Chemical reactions of Fe and Al particle surfaces with the atmosphere and the milling media lead to the formation of highly porous hydroxides on the particle surfaces. Hence the specific surface area of the powders increases, while the powder density decreases during milling. The fraction of Fe oxidized during milling was determined to be 0.13. The fraction of Al oxidized during milling strongly depends on the metal content of the powder mixture. It ranges between 0.4 and 0.8.     

Dissolution and Dispersion Behavior of Barium Carbonate in Aqueous Suspensions

Dissolution of BaCO₃ and its effect on the dispersion behavior of aqueous BaCO₃ suspensions at various pH values have been investigated. The amount of leached Ba²⁺ decreases with increasing pH value, which agrees with thermodynamically calculated results. The dissolution of BaCO₃ also causes an increase in pH value of the suspension, but the change decreases with increasing initial pH value. The isoelectric point (IEP) of leached BaCO₃ powder is at a pH of ∼10–10.5 and remains unchanged with increasing solids loading. The IEP of BaCO₃ shows no significant change with added KCl or K₂CO₃, but shifts to a higher pH with increasing concentration of added BaCl₂.     

Fabrication and Characterization of an Ultra-High-Temperature Carbon Fiber-Reinforced ZrB2–SiC Matrix Composite

A novel carbon fiber-reinforced ZrB₂–SiC matrix composite was fabricated by heaterless chemical vapor infiltration through infiltration of SiC matrix into a carbon fiber-ZrB₂ powder preform. The C/ZrB₂–SiC composite presented a flexural strength of 148 MPa, a fracture toughness of 5.6 MPa·m^1/2, and a good oxidation and ablation resistance.