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.     

Anisotropy of Mechanical Properties in a Hot‐Pressed Boron Carbide

Effects of microstructure and material properties on the mechanical behavior of hot‐pressed boron carbide are presented. The microstructure and intrinsic microstructural inhomogeneities have been characterized using scanning electron microscopy characterization techniques (SEM/EDS/EBSD). In situ mechanical characterizations of the boron carbide microstructure and its larger inhomogeneities have been performed by nanoindentation. Macroscopic dynamic and quasi‐static compressive responses have been studied in two characteristic orientations (parallel and perpendicular to the hot‐pressing direction) using a modified compression Kolsky bar setup (strain rates of /s) and standard MTS test machine (strain rates of /s). The microstructure characterization showed that boron carbide has a fine‐grained microstructure with a complex superposition of nonmetallic inclusions, such as free carbon, AlN, and BN. Nanoindentation tests conducted in three principal planes of the plate revealed an anisotropy of the mechanical properties. The compression tests revealed that the strength of this hot‐pressed boron carbide is orientation dependent. Detailed SEM analysis indicated transgranular fracture and microcracking originating at large carbon inclusions. Influences of microstructural anisotropy on the mechanical response of the material are discussed.     

Microstructural Characterization of a Commercial Hot‐Pressed Boron Carbide Armor Plate

Detailed microstructural characterization was carried out on a commercial‐grade hot‐pressed boron carbide armor plate. The boron carbide grains have close to B₄C stoichiometry, and most of them have no planar defects. The most prominent second phase is intergranular graphite inclusions that are surrounded by multiple boron carbide grains. Submicrometer intragranular and intergranular BN and AlN precipitates were also observed. In addition, fine dispersions of AlN nanoprecipitates were observed in some but not all grains. No intergranular films were found. These microstructural characteristics are compared with the lab‐consolidated boron carbide and their effects on the mechanical properties of boron carbide are addressed.     

Densification and Thermal Stability of Hot‐Pressed Si3N4–ZrB2 Ceramics

Densification and thermal stability of hot‐pressed Si₃N₄–ZrB₂ ceramics with and without additives were investigated in N₂ atmosphere. The addition of MgO–Yb₂O₃, MgO–Y₂O₃, and Al₂O₃–Yb₂O₃ resulted in significant increase in relative density of the ceramics hot‐pressed at 1500°C from 48.5% to 98.0%, 97.3%, and 95.6%, respectively. There was weak reaction of ZrB₂ with N₂ to form ZrN in hot‐pressed ceramics. Then heat treatment at 1550°C resulted in the further reactions to produce ZrN, ZrSi₂, and BN. The Si₃N₄–ZrB₂ ceramics with MgO–Yb₂O₃ showed much better thermal stability as compared to the ceramics with Al₂O₃–Yb₂O₃. The small difference in density led to the obvious difference in thermal stability. Therefore, Si₃N₄–ZrB₂ ceramics should be densified to full density, to obtain high thermal stability.     

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.     

Densification Behavior,Phase Transition,and Preferred Orientation of Hot‐Pressed ZnS Ceramics from Precipitated Nanopowders

In this study, transparent ZnS ceramics were hot pressed from precipitated wurtzite nanopowders. Influences of sintering temperature on wurtzite‐to‐sphalerite phase transition and densification behavior have been investigated. Maximum sphalerite phase content and highest densification were simultaneously obtained in the sample hot pressed at 900°C with uniaxial pressure of 250 MPa for 2 h, which accounts for the highest transmittance above 55% and 70% in the range 2–5 μm and 5–13 μm, respectively. Preferred orientation of wurtzite grains in [002] direction paralleled to the press direction was also observed, which is supposed to be benefit to transmittance by reducing birefraction and second‐phase scattering. Furthermore, second‐phase scattering caused by wurtzite grains has been investigated. It is found that fine grains are conducive to hot‐pressed ZnS ceramics with high transmittance, especially in the short‐wavelength range.     

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.     

Optical Characterizations of Hot‐Pressed Erbium‐Doped Calcium Fluoride Transparent Ceramic

Nanoparticles of erbium‐doped calcium fluoride were synthesised by the coprecipitation method. Micromorphology of the obtained nanoparticles was observed by transmission electron microscopy. The nanoparticles were hot‐pressed in a vacuum environment to achieve Er:CaF₂ transparent ceramic. X‐ray diffraction analysis confirmed the crystallization of a single fluorite phase after sintered. Transmittance spectrum of Er:CaF₂ ceramic sample was measured, and the transmittance at 1200 nm reached about 87%. Microstructures were characterized using field‐emission scanning electron microscopy. The luminescence spectrum of Er:CaF₂ transparent ceramics under 488‐ and 978‐nm excitation was measured and discussed. It was evidenced that strong cross‐relaxation processes between Er³⁺ ions occur at high dopant concentration, and favoring the red emission at the expense of the green one.     

Sintering Mechanisms and Kinetics for Reaction Hot‐Pressed ZrB2

Sintering mechanisms and kinetics were investigated for ZrB₂ ceramics produced using reaction hot pressing. Specimens were sintered at temperatures ranging from 1800°C to 2100°C for times up to 120 min. ZrB₂ was the primary phase, although trace amounts of ZrO₂ and C were also detected. Below 2000°C, the densification mechanism was grain‐boundary diffusion with an activation energy of 241 ± 41 kJ/mol. At higher temperatures, the densification mechanism was lattice diffusion with an activation energy of 695 ± 62 kJ/mol. Grain growth exponents were determined to be ~4.5, which indicated that a grain pinning mechanism was active in both temperature regimes. The diffusion coefficients for grain growth were 1.5 × 10^?16 cm⁴/s at 1900°C and 2.1 × 10^?15 cm⁴/s at 2100°C. This study revealed that dense ZrB₂ ceramics can be produced by reactive hot pressing in shorter times and at lower temperatures than conventional hot pressing of commercial powders.     

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.     

The Effect of Relative Density on the Mechanical Properties of Hot‐Pressed Cubic Li7La3Zr2O12

The effect of relative density on the hardness and fracture toughness of Al‐substituted cubic garnet Li_6.19Al_0.27La₃Zr₂O₁₂ (LLZO) was investigated. Polycrystalline LLZO was made using solid‐state synthesis and hot‐pressing. The relative density was controlled by varying the densification time at fixed temperature (1050°C) and pressure (62 MPa). After hot‐pressing, the average grain size varied from approximately 2.7–3.7 μm for the 85% and 98% relative density samples, respectively. Examination of fracture surfaces revealed a transition from inter‐ to intragranular fracture as the relative density increased. The Vickers hardness increased with relative density up to 96%, above which the hardness was constant. At 98% relative density, the Vickers hardness was equal to the hardness measured by nanoindentation 9.1 GPa, which is estimated as the single‐crystal hardness value. An inverse correlation between relative density and fracture toughness was observed. The fracture toughness increased linearly from 0.97 to 2.37 MPa√m for the 98% and 85% relative density samples, respectively. It is suggested that crack deflection along grain boundaries can explain the increase in fracture toughness with decreasing relative density. It was also observed that the total ionic conductivity increased from 0.0094 to 0.34 mS/cm for the 85%–98% relative density samples, respectively. The results of this study suggest that the microstructure of LLZO must be optimized to maximize mechanical integrity and ionic conductivity.     

Ceramics Based on Reactively Sintered Boron Carbide

Refractories and Industrial Ceramics - The influences of various processing parameters on phase and structure formation during reactive sintering of B4C materials in a Si melt are studied. The...     

Ultra‐High Temperature Mechanical Properties of a Zirconium Diboride–Zirconium Carbide Ceramic

The mechanical properties of a ZrB₂‐10 vol% ZrC ceramic were measured up to 2300°C in an argon atmosphere. Dense billets of ZrB₂‐9.5 vol% ZrC‐0.1 vol% C were produced by hot‐pressing at 1900°C. The ZrB₂ grain size was 4.9 μm and ZrC cluster size was 1.8 μm. Flexure strength was 695 MPa at ambient, decreasing to 300 MPa at 1600°C, increasing to 345 MPa at 1800°C and 2000°C, and then decreasing to 290 MPa at 2200°C and 2300°C. Fracture toughness was 4.8 MPa·m^½ at room temperature, decreasing to 3.4 MPa·m^½ at 1400°C, increasing to 4.5 MPa·m^½ at 1800°C, and decreasing to 3.6 MPa·m^½ at 2300°C. Elastic modulus calculated from the crosshead displacement was estimated to be 505 GPa at ambient, relatively unchanging to 1200°C, then decreasing linearly to 385 GPa at 1600°C, more slowly to 345 GPa at 2000°C, and then more rapidly to 260 GPa at 2300°C. Surface flaws resulting from machining damage were the critical flaw up to 1400°C. Above 1400°C, plasticity reduced the stress at the crack tip and the surface flaws experienced subcritical crack growth. Above 2000°C, microvoid coalescence ahead of the crack tip caused failure.     

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.     

Microstructure and Li‐Ion Conductivity of Hot‐Pressed Cubic Li7La3Zr2O12

The effect of hot‐pressing temperature on the microstructure and Li‐ion transport of Al‐doped, cubic Li₇La₃Zr₂O₁₂ (LLZO) was investigated. At fixed pressure (62 MPa), the relative density was 86%, 97%, and 99% when hot‐pressing at 900°C, 1000°C, and 1100°C, respectively. Electrochemical impedance spectroscopy showed that the percent grain‐boundary resistance decreased with increasing hot‐pressing temperature. Hot pressing at 1100°C resulted in a total conductivity of 0.37 mS/cm at room temperature where the grain boundaries contributed to 8% of the total resistance; one of the lowest grain‐boundary resistances reported. We believe hot pressing is an appealing technique to minimize grain‐boundary resistance and enable correlations between LLZO composition and bulk ionic conductivity.     

Mechanical,Tribological, and Thermal Properties of Hot‐Pressed ZrB2‐B4C Composite

The effect of addition of submicrometer‐sized B₄C (5,10 and 15 wt%) on microstructure, phase composition, hardness, fracture toughness, scratch resistance, wear resistance, and thermal behavior of hot‐pressed ZrB₂‐B₄C composites is reported. ZrB₂‐B₄C (10 wt%) composite has V_H1 of 20.81 GPa and fracture toughness of 3.93 at 1 kgf, scratch resistance coefficient of 0.40, wear resistance coefficient of 0.01, and ware rate of 0.49 × 10^?3 mm³/Nm at 10N. Crack deflection by homogeneously dispersed submicrometer‐sized B₄C in ZrB₂ matrix can improve the mechanical and tribological properties. Thermal conductivity of ZrB₂‐B₄C composites varied from 70.13 to 45.30 W/m K between 100°C and 1000°C which is encouraging for making ultra‐high temperature ceramics (UHTC) component.     

Synthesis of Biopolymer‐Derived Zirconium Carbide Powder by Facile One‐Pot Reaction

Zirconium carbide (ZrC) was synthesized by polycondensation and carbothermal reduction reactions from an organic–inorganic hybrid complex. A natural biopolymer Gum Karaya (GK) and zirconyl oxychloride octahydrate (ZOO) were used as the sources of carbon and zirconium, respectively. FTIR of as‐synthesized dried complexes revealed formation of Zr–O. Pyrolysis of the complexes at 1200°C/1 h under argon resulted in tetragonal and monoclinic zirconia which after heat treatment at 1400°C–1550°C transformed to zirconium carbide. Thermal analysis shows that the GK–ZOO complexes lost less mass than the pristine GK to 600°C. The intensity of exothermic decomposition decreases and shifted to higher temperature for the hybrid complexes indicating that zirconia induced thermal stability. A maximum ZrC yield of ~60 wt% is obtained for the intermediate GK–ZOO ratio of 1:2. Particles pyrolyzed for 1 h at 1550°C were coarser (5–10 μm) with flakes for lower GK–ZOO weight ratio, but were spheroidal with narrow size distribution (~1 μm) with increasing GK–ZOO weight ratio.     

Densification and Properties of α-Silicon Carbide

Densification of a-Sic powders with no premixed sintering aids (type 1) and with premixed B and C (type 2) was investigated by sintering them at 2150° to 2200°C for 30 min. Flexure strengths, Weibull moduli, and fracture flaws were characterized for type 2 α-SiC only. The results were compared with those for a state-of-the-art sintered a-Sic material.     

Palladium Migration Through a Zirconium Carbide Coating in TRISO‐Coated Fuel Particles

Reaction of ZrC with Pd at temperatures up to 1500°C was examined using ZrC/Pd composite, Pd/ZrC‐coated TRISO particles, and Pd/ZrC bulk diffusion couples experiments. Intermetallic phase (Pd₃Zr) and amorphous carbon at the ZrC–Pd interfaces were identified by X‐ray diffraction (XRD), Raman and scanning electron microscope (SEM). Moreover, thicknesses of Pd₃Zr layers were measured by energy‐dispersive X‐ray spectrometry (EDS). The validity of the reaction was proved by thermodynamic calculation. The reaction kinetics parameters, i.e., the activation energy (208.2–266.5 kJ/mol) and the reaction order (3.38–3.78) for Pd attacking through a ZrC coating in TRISO particles were determined based on both the DSC curves and the growth of the Pd₃Zr layer.     

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.