Pressureless Sintering of Zirconium Diboride Using Boron Carbide and Carbon Additions

The synergistic roles of boron carbide and carbon additions in the enhanced densification of zirconium diboride (ZrB₂) by pressureless sintering have been studied. ZrB₂ was sintered to >99% relative density at 1900°C. The combination of 2 wt% boron carbide and 1 wt% carbon promoted densification by removing surface oxide impurities (ZrO₂ and B₂O₃) and inhibiting grain growth. Four-point bending strength (473±43 MPa), Vickers' microhardness (19.6±0.4 GPa), fracture toughness (3.5±0.6 MPa·m^1/2), and Young's modulus (507 GPa) were measured. Thermal gravimetry showed that the combination of additives did not have an adverse effect on the oxidation behavior.     

Pressureless Sintering of Zirconium Diboride

Zirconium diboride (ZrB₂) ceramics were sintered to a relative density of ∼98% without applied external pressure. Densification studies were performed in the temperature range of 1900°–2150°C. Examination of bulk density as a function of temperature revealed that shrinkage started at ∼2100°C, with significant densification occurring at only 2150°C. At 2150°C, isothermal holds were used to determine the effect of time on relative density and microstructure. For a hold time of 540 min at 2150°C, ZrB₂ pellets reached an average density of 6.02±0.04 g/cm³ (98% of theoretical) with an average grain size of 9.0±5.6 μm. Four-point bend strength, elastic modulus, and Vickers' hardness were measured for sintered ZrB₂ and compared with values reported for hot-pressed materials. Vickers' hardness of sintered ZrB₂ was 14.5±2.6 GPa, which was significantly lower when compared with 23 GPa for hot-pressed ZrB₂. Strength and elastic modulus of the ZrB₂ were 444±30 MPa and 454 GPa, which were comparable with values reported for hot-pressed ZrB₂. The ability to densify ZrB₂ ceramics without hot pressing should enable near-net shape processing, which would significantly reduce the cost of fabricating ZrB₂ components compared with conventional hot pressing and machining.     

Pressureless Sintering of Boron Carbide

B₄C powder compacts were sintered using a graphite dilatometer in flowing He under constant heating rates. Densification started at 1800°C. The rate of densification increased rapidly in the range 1870°–2010°C, which was attributed to direct B₄C–B₄C contact between particles permitted via volatilization of B₂O₃ particle coatings. Limited particle coarsening, attributed to the presence or evolution of the oxide coatings, occurred in the range 1870°–1950°C. In the temperature range 2010°–2140°C, densification continued at a slower rate while particles simultaneously coarsened by evaporation–condensation of B₄C. Above 2140°C, rapid densification ensued, which was interpreted to be the result of the formation of a eutectic grain boundary liquid, or activated sintering facilitated by nonstoichiometric volatilization of B₄C, leaving carbon behind. Rapid heating through temperature ranges in which coarsening occurred fostered increased densities. Carbon doping (3 wt%) in the form of phenolic resin resulted in more dense sintered compacts. Carbon reacted with B₂O₃ to form B₄C and CO gas, thereby extracting the B₂O₃ coatings, permitting sintering to start at ∼1350°C.     

Aqueous Gelcasting and Pressureless Sintering of Zirconium Diboride Ceramics

Dense (97.3%) zirconium diboride (ZrB₂) ceramics were obtained via gelcasting and pressureless sintering. Four wt% B₄C was used as sintering aid. ZrB₂, SiC, and B₄C can codisperse well in the alkaline region, using a polyacrylate dispersant. Compared with monolithic ZrB₂ (Z), the mechanical properties of ZrB₂‐SiC (ZS) were enhanced. The Vickers hardness and fracture toughness of ZS were (13.1 ± 0.6) GPa and (2.5 ± 0.4) MPa m^1/2, respectively.     

Nickel–Boron Nanolayer-Coated Boron Carbide Pressureless Sintering

Sintering of pure B₄C and Ni₂B nanolayer-coated B₄C was studied from 1300° to 1600°C, with the holding time at the peak temperatures being 2 or 10 h. Compacts were made by uniaxial die compaction and combustion-driven compaction. Pure B₄C sample shows less sintering at all conditions. Ni₂B-coated B₄C sample shows more extensive densification, neck formation, and grain shape accommodation. The combustion driven compaction process accelerates sintering by offering higher green density to start with. The Ni₂B species on the B₄C particle surfaces melts into a nickel–boron-containing liquid phase during heating, remains as liquid during sintering, and then transforms into Ni₄B₃ and NiB during cooling. High-resolution composition analysis shows that there is no nickel diffusion into bulk B₄C during the sintering process. However, there is boron diffusion into the Ni₂B coating layer. Carbon diffusion cannot be directly measured but is believed to be a simultaneous process as boron diffusion. A multievent sintering process has been proposed to explain the observations.     

Effect of Iron and Boron Carbide on the Densification and Mechanical Properties of Titanium Diboride Ceramics

The effect of Fe and B₄C on the sintering behavior and mechanical properties of TiB₂ ceramics have been studied. Sintering was performed in an Ar atmosphere at 2000° using attrition-milled TiB₂ powder (mean particle size = 0.8 μm). When a small amount of Fe (0.5 wt%) was added, abnormal grain growth occurred and the sintered density was low. In the case of B₄C added along with 0.5 wt% Fe, however, abnormal grain growth was remarkably suppressed, and the sintered density was increased up to 95% of theoretical. But with excess Fe addition (5 wt%), B₄C grains did not act as a grain growth inhibitor, and B₄C grains were frequently trapped in large TiB₂ grains. The best mechanical properties were obtained for the TiB₂–10 wt% B₄C–0.5 wt% Fe ceramics, which exhibited a three-point bending strength of 400 MPa and a fracture toughness of 5.5 MPa · m^1/2.     

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 Zirconium Diboride: Particle Size and Additive Effects

Zirconium diboride (ZrB₂) was densified by pressureless sintering using <4-wt% boron carbide and/or carbon as sintering aids. As-received ZrB₂ with an average particle size of ∼2 μm could be sintered to ∼100% density at 1900°C using a combination of boron carbide and carbon to react with and remove the surface oxide impurities. Even though particle size reduction increased the oxygen content of the powders from ∼0.9 wt% for the as-received powder to ∼2.0 wt%, the reduction in particle size enhanced the sinterability of the powder. Attrition-milled ZrB₂ with an average particle size of <0.5 μm was sintered to nearly full density at 1850°C using either boron carbide or a combination of boride carbide and carbon. Regardless of the starting particle size, densification of ZrB₂ was not possible without the removal of oxygen-based impurities on the particle surfaces by a chemical reaction.     

Effect of Zirconium on the Densification of Reactively Hot‐Pressed Zirconium Carbide

Densification mechanisms involved during reactive hot pressing (RHP) of zirconium carbide (ZrC) have been studied. RHP has been carried out using zirconium (Zr) and graphite (C) powders in the molar ratios 1:0.5, 1:0.67, 1:0.8, and 1:1 at 40 MPa, 800°C–1200°C for different durations. The volume fractions of phases formed, including porosity, are determined from the measured density and from Rietveld analysis. Increased densification with an increasing nonstoichiometry in carbon has been observed. Microstructural and X‐ray diffraction observations coupled with the predictions of a model based on the constitutive laws governing plastic flow of zirconium suggest that the better densification of nonstoichiometric compositions arise from the higher amount of starting Zr and also the longer duration of its availability for plastic flow during RHP. Volume shrinkage due to reaction between Zr and C and the gradual elimination of the soft metal phase limit the final density achievable. Based on these observations, a two‐step RHP carried out at 800°C and 1200°C leads to a better densification than a single RHP at 1200°C.     

Electrical Resistivity of Titanium Diboride and Zirconium Diboride

The electrical resistivities of hot-pressed samples of Ti_{1- x} Zr _x B₂ ( x = 0.0, 0.3, 0.5, 0.7, 1.0) were measured by a four-point ac technique over the range 298 to 1573 K in an argon atmosphere. The hot-pressed samples for the intermediate compositions were found to be mixtures of two solid-solution phases. The resistivities for all compositions were found to increase linearly with temperature and can be described by ρ( T ) =ρ₂₉₈+φ( T - 298). The room-temperature resistivity ρ298 (μΩ cm) and the temperature coefficient of resistivity φ (nΩ·cm/K) for ZrB₂ were determined to be 7.8 and 10, both of which increase with the content of TiB₂. These values for TiB₂ were determined to be 20.4 and 36, respectively.     

Zirconium Diboride with High Thermal Conductivity

Thermal properties were characterized for zirconium diboride produced by reactive hot pressing and compared to ZrB₂ ceramics that were hot pressed from commercial powders. No sintering additives were used in either process. Thermal conductivity was calculated from measured values of heat capacity, thermal diffusivity, and density for temperatures ranging from 298 to 2273 K. ZrB₂ produced by reactive hot pressing achieved near full density, but had a small volume fraction of ZrO₂, whereas hot‐pressed ZrB₂ contained porosity and carbon inclusions. Reactive hot pressing produced a ceramic with higher thermal diffusivity and heat capacity, resulting in thermal conductivities of 127 W·(m·K)^?1 at 298 K and 80 W·(m·K)^?1 at 2273 K, which were up to ~30% higher than typically reported for hot‐pressed ZrB₂.     

Effect of Carbon and Oxygen on the Densification and Microstructure of Hot Pressed Zirconium Diboride

The role of carbon additions and oxygen content on the densification of zirconium diboride (ZrB₂) was studied. ZrB₂ with up to 1 wt% added carbon was hot pressed at temperatures of 2000°C and 2100°C. Nominally pure ZrB₂ hot pressed at 2100°C achieved relative densities >95.5%. Carbon and oxygen analysis indicate that oxygen removal was facilitated by the reduction of oxides with carbon or the removal of boria (B₂O₃) as a vapor. Therefore, by removing oxides from the particle surfaces, carbon additions of ≥0.5 wt% enabled densification to proceed to >96.5% of theoretical at 2000°C. Raman spectroscopy revealed the formation of boron carbide (B_4.3C) in specimens with carbon additions of ≥0.75 wt%. The formation of B_4.3C was eliminated via a 1 wt% addition of zirconium hydride (ZrH₂), as a source of zirconium, resulting in the formation of carbon as the only residual second phase. Grain sizes were in the range of 7–10 μm (2000°C) and 12–16 μm (2100°C) and only appeared to be controlled by temperature, as no trends due to the evaluated carbon or oxygen contents were observed.     

Hot Isostatic Pressing of Silicon Nitride with Boron Nitride, Boron Carbide, and Carbon Additions

Si₃ N₄ test bars containing additions of BN, B₄C, and C, were hot isostatically pressed in Ta cladding at 1900° and 2050°C to 98.9% to 99.5% theoretical density. Room-temperature strength data on specimens containing 2 wt% BN and 0.5 wt% C were comparable to data obtained for Si₃ N₄ sintered with Y₂O₃, Y₂O₃ and Al₂O₃, or ZrO₂. The 1370°C strengths were less than those obtained for additions of Y₂O₃ or ZrO₂ but greater than those obtained from a combination of Y₂O₃ and Al₂O₃. Scanning electron microscope fractography indicated that, as with other types of Si₃N₄, roomtemperature strength was controlled by processing flaws. The decrease in strength at 1370°C was typical of Si₃N₄ having an amorphous grainboundary phase. The primary advantage of non-oxide additions appears to be in facilitating specimen removal from the Ta cladding.     

Oxidation Behavior of Zirconium Diboride Silicon Carbide Produced by the Spark Plasma Sintering Method

Dense samples of ZrB₂–20 vol% SiC were successfully fabricated by spark plasma sintering without the use of sintering aids. Oxidation behavior of these samples was characterized by exposing them to 1400°, 1500°, and 1600°C in an ambient atmosphere for 150 min, and by measuring the weight gains of the sample and crucible, as well as the thickness of the oxide scale and the glassy outer layer. The effects of gravity on the viscous outer layer are shown to result in significant heterogeneity within a sample. The oxidation scales were characterized by scanning electron microscopy and transmission electron microscopy with energy dispersive spectroscopy analysis. The oxide scale was found to be composed of three layers: (1) a SiO₂-rich glassy outer layer, (2) an intermediate layer of a ZrO₂ matrix with interpenetrating SiO₂, and (3) a layer containing a ZrO₂ matrix enclosing partially oxidized ZrB₂ with Si–C–B–O glass inclusions.     

Hot‐Pressing Kinetics and Densification Mechanisms of Boron Carbide

The hot‐pressing kinetics of boron carbide at different stages in the hot‐pressing process was investigated. Based general densification equation and pore‐dragged creep model, the densification and grain growth kinetics were analyzed as a function of various parameters such as sintering temperature, sintering pressure and dwell time. Stress exponent of n ≈ 3 at the initial dwell stage suggests the plastic deformation may dominates the densification. The further TEM observations and the calculation based on effective stress and plastic yield stress also indicate that plastic deformation may occur and account for the large increase in density at the initial stage of sintering. Calculated grain size exponent of m ≈ 3 suggests that the grain‐boundary diffusion dominates the densification at the final stage. During the final stage of sintering, grain growth may be determined by evaporation/condensation and grain‐boundary migration.     

Microstructure of Platelet-Reinforced Ceramics Prepared by the Directed Reaction of Zirconium with Boron Carbide

The microstructure of a ZrB₂-platelet-reinforced ZrC _x composite was examined using transmission electron microscopy and X-ray diffraction. The composites, which are formed by the reaction of molten Zr with B₄C, contain a small amount of residual Zr, the amount of which can be varied by altering the processing conditions. Results on two different materials are reported, one with a low Zr content, ∼2.5 vol%, and the other with a very low Zr content, ∼0.5 vol%. In the former, metallic Zr was found at triple points and as a grain boundary phase between the boride and carbide, and to a lesser degree between the boride grains. In the latter, it was only found as a ternary Zr–ZrB₂–ZrC _x eutectic at the triple points. Both materials showed a nearly random distribution of the boride and carbide constituents, though specific crystallographic relationships were found between the various constituents.     

Aqueous Tape Casting of Zirconium Diboride

Aqueous tape casting of ZrB₂ powder with sintering additives was investigated. The dispersion of ZrB₂ suspensions in aqueous media was studied and characterized in terms of zeta potential, sedimentation, and rheological measurements. A well-stabilized suspension with a high solid content (up to 45 vol%) was prepared in the alkaline pH region with 0.4 wt% Lopon 885 as the dispersant. Several suspensions with different compositions of binder and plasticizer were prepared for comparison. Crack-free green tapes with a maximum thickness of approximately 250 μm were obtained with a binder content of 18–23 wt%. The green tapes had high qualities, such as homogeneity, good flexibility, and a smooth surface. Results showed that the slurries at selected formulations met the needs of the tape-casting process.     

Boron Carbide–Zirconium Boride In Situ Composites by the Reactive Pressureless Sintering of Boron Carbide–Zirconia Mixtures

The heating of B₄C–YTZP (where YTZP denotes yttria-stabilized zirconia polycrystals) mixtures, under an argon atmosphere, generates B₄C–ZrB₂ composites, because of a low-temperature (<1500°C) carbide–oxide reaction. Composites derived from mixtures that include ≥15% YTZP are better sintered than monolithic B₄C that has been fired under the same conditions. Firing to ∼2160°C (1 h dwell) generates specimens with a bulk density of ≥91% of the theoretical density (TD) for cases where the initial mixture includes ≥15% YTZP. Mixtures that include 30% YTZP allow a fired density of ≥97.5% TD to be attained. The behavior of the B₄C–YTZP system is similar to that of the B₄C–TiO₂ system. Dense B₄C–ZrB₂ composites attain a hardness (Vickers) of 30–33 GPa.     

二硼化锆系复合材料研究进展

ZrB2系复合材料具有高熔点、高硬度、高导热率等优良性能，是一种性能优异的高温结构材料，具有广泛的应用前景。本文概述了ZrB2基复合材料．如：ZrB2-Ni，ZrB2-SiC，ZrB2／B4C-Ni等的研究现状，并对其力学性能进行了评价；总结了近年来国内外在ZrB2基复合材料烧结工艺方面的研究进展。     

Microstructure Study on Oxidation of Zirconium Diboride

The oxidation behaviors of fused zirconium diboride and chemosynthetic zirconium diboride as well as morphology and composition of their oxidation products were researched by FESEM-EDS and XRD. The two kinds of zirconium diboride were heated at 700 ℃, 900 ℃, 1 100 ℃ and 1 300 ℃ for 3 h in air, respectively. The results show that ZrO_2 and B_2O_3(l) are generated from the chemosynthetic zirconium diboride oxidized at 700 ℃ for 3 h or the fused zirconium diboride oxidized at 800 ℃ for 24 h; B_2O_3(l) dissolves into water and then H_3BO_3 crystallizes.