Effect of SiC on Interfacial Reaction and Sintering Mechanism of TiB2

Compacts of TiB₂ with densities approaching 100% are difficult to obtain using pressureless sintering. The addition of SiC was very effective in improving the sinterability of TiB₂. The oxygen content of the raw TiB₂ powder used in this research was 1.5 wt%. X-ray photoelectron spectroscopy showed that the powder surface consisted mainly of TiO₂ and B₂O₃. Using vacuum sintering at 1700°C under 13–0.013 Pa, TiB₂ samples containing 2.5 wt% SiC achieved 96% of their theoretical density, and a density of 99% was achieved by HIPing. TEM observations revealed that SiC reacts to form an amorphous phase. TEM-EELS analysis indicated that the amorphous phase includes Si, O, and Ti, and X-ray diffraction showed the reaction to be TiO₂+ SiC → SiO₂+ TiC. Therefore, the improved sinterability of TiB₂ resulted from the SiO₂ liquid phase that was formed during sintering when the raw TiB₂ powder had 1.5 wt% oxygen.     

Preparation and Microstructure of a ZrB2–SiC Composite Fabricated by the Spark Plasma Sintering–Reactive Synthesis (SPS–RS) Method

A mixture of Zr, B₄C, and Si powders was adopted to synthesize a ZrB₂–SiC composite using the spark plasma sintering–reactive synthesis (SPS–RS) method. SPS treatments were carried out in the temperature range of 1350°–1500°C under a varying pressure of 20–65 MPa with a 3-min holding time. A dense (∼98.5%) ZrB₂–SiC composite was successfully fabricated at 1450°C for 3 min under 30 MPa. The microstructure of the composite was investigated. The in situ formed ZrB₂ and SiC phases dispersed homogeneously on the whole. The grain size of ZrB₂ and SiC was <5 and 1 μm, respectively. A number of in situ formed ultrafine SiC particles were observed entrapped in the ZrB₂ grains.     

Joining of Carbon—Carbon Composites Using Boron and Titanium Disilicide Interlayers

The feasibility of joining of 3-D carbon—carbon (C–C) composites by using B and TiSi₂ interlayers has been investigated. The optimum temperature for joining with a B interlayer was determined to be about 1995°C and that for joining with a TiSi₂ interlayer was about 1490°C. The shear strengths of the joints made at these optimum temperatures were found to increase with the shear testing temperature up to a point, followed by a decrease at higher temperatures. For C–C specimens bonded at 1995°C with a B interlayer, the maximum joint shear strength (average value 18.35 MPa) was observed at the test temperature of 1660°C. The shear strength of joints produced with a TiSi₂ interlayer showed a maximum at the test temperature of 1164°C, with an average value of 34.41 MPa. The B interlayers reacted with C–C composite pieces during joining, and the product of reaction was identified as B₄C. In specimens joined with TiSi₂ interlayers, the reaction between TiSi2 and C did not go to completion, and the bond interlayer contained TiC, SiC, and TiSi₂.     

Oxidation Resistance of Fully Dense ZrB2 with SiC, TaB2, and TaSi2 Additives

Specimens of ZrB₂ containing various concentrations of B₄C, SiC, TaB₂, and TaSi₂ were pressureless-sintered and post-hot isostatic pressed to their theoretical densities. Oxidation resistances were studied by scanning thermogravimetry over the range 1150°–1550°C. SiC additions improved oxidation resistance over a broadening range of temperatures with increasing SiC content. Tantalum additions to ZrB₂–B₄C–SiC in the form of TaB₂ and/or TaSi₂ increased oxidation resistance over the entire evaluated spectrum of temperatures. TaSi₂ proved to be a more effective additive than TaB₂. Silicon-containing compositions formed a glassy surface layer, covering an interior oxide layer. This interior layer was less porous in tantalum-containing compositions.     

Microstructure and Mechanical Properties of In Situ Produced TiC/TiB2/MoSi2 Composites

A novel microstructure of in situ produced TiC/TiB₂/MoSi₂ composite and its mechanical properties were investigated. The results indicate that TiC/TiB₂/MoSi₂ composites can be fabricated by reactive hot pressing the mixed powders of MoSi₂, B₄C, and Ti. A novel microstructure consisting of hollow particles of TiC and TiB₂ grains in an MoSi₂ matrix was obtained. Grains of in situ produced TiC and TiB₂ were much finer, from 100 to 400 nm. During the fracture process, hollow particles relieved crack tip stress, encouraging crack branching and changing the original direction of the main crack. The highest bending strength of this composite achieved was 480 MPa, twice that of monolithic MoSi₂, and the greatest fracture toughness of the composite reached 5.2 MPa·m^1/2.     

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.     

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.     

Reactive Hot Pressing of ZrB2–SiC Composites

A ZrB₂–SiC composite was prepared from a mixture of zirconium, silicon, and B₄C via reactive hot pressing. The three-point bending strength was 506 ± 43 MPa, and the fracture toughness was 4.0 MPa·m^1/2. The microstructure of the composite was observed via scanning electron microscopy; the in-situ -formed ZrB₂ and SiC were found in agglomerates with a size that was in the particle-size ranges of the zirconium and silicon starting powders, respectively. A model of the microstructure formation mechanism of the composite was proposed, to explain the features of the phase distributions. It is considered that, in the reactive hot-pressing process, the B and C atoms in B₄C will diffuse into the Zr and Si sites and form ZrB₂ and SiC in situ , respectively. Because the diffusion of Zr and Si atoms is slow, the microstructure (phase distributions) of the obtained composite shows the features of the zirconium and silicon starting powders.     

In Situ Synthesis of Ultrafine ZrB2–SiC Composite Powders and the Pressureless Sintering Behaviors

Ultrafine ZrB₂–SiC composite powders have been synthesized in situ using carbothermal reduction reactions via the sol–gel method at 1500°C for 1 h. The powders synthesized had a relatively smaller average crystallite size (<200 nm), a larger specific surface area (∼20 m²/g), and a lower oxygen content (∼1.0 wt %). Composites of ZrB₂+20 wt% SiC were pressureless sintered to ∼96.6% theoretical density at 2250°C for 2 h under an argon atmosphere using B₄C and Mo as sintering aids. Vickers hardness and flexural strength of the sintered ceramic composites were 13.9±0.3 GPa and 294±14 MPa, respectively. The microstructure of the composites revealed that elongated SiC grain dispersed uniformly in the ZrB₂ matrix. Oxidation from 1100° to 1600°C for 30 min showed no decrease in strength below 1400°C but considerable decrease in strength with a rapid weight increment was observed above 1500°C. The formation of a protective borosilicate glassy coating appeared at 1400°C and was gradually destroyed in the form of bubble at higher temperatures.     

Low-Temperature Densification of TiN–TiB2 Composites Through Reactive Hot Pressing with Excess Ti Additions

Reactive hot pressing of Ti and BN powder mixtures is used to produce dense TiN _x –TiB₂ composites. The effect of excess Ti along with a small addition, ∼1 wt% Ni, on the reaction and densification of the composite was investigated. A composite of ∼99.9% relative density (RD) was produced at 1200°C at 40 MPa for 30 min with 1 wt% Ni, whereas composites produced without Ni are porous and contain residual reactants. The microstructural studies on composite samples with excess Ti produced at short durations indicate the presence of a transient (Ni–Ti) phase from which Ti is finally removed to form substoichiometric TiN _x . The hardness of the dense TiN _x –TiB₂ composite is ∼22 GPa. The densification mechanism in this system is contrasted with the role of nonstoichiometry in the Zr–B₄C system.     

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.     

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.     

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.     

Properties of ZrB2–SiC Ceramics by Pressureless Sintering

Pressureless sintering was used to densify ZrB₂–SiC ultra-high temperature ceramics. The physical, mechanical, thermal, electrical, and high temperature properties were investigated. This comprehensive set of properties was measured for ZrB₂ containing 20 vol% SiC in which B₄C and C were used as the sintering aids. The three-point flexural strength was 361±44 MPa and the elastic modulus was 374±25 GPa. The Vickers hardness and fracture toughness were 14.7±0.2 GPa and 4.0±0.5 MPa·m^1/2 respectively. Scanning electron microscopy studies of the microstructure of ZrB₂–SiC showed that SiC particles were distributed homogenously in the ZrB₂ matrix with little residual porosity.     

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.     

Corrosion of Ceramics in Aqueous Hydrofluoric Acid

A variety of commercially available ceramic-based oxides, carbides, nitrides, and borides were evaluated for chemical attack in an azeotropic aqueous hydrofluoric acid (HF) test protocol at 90°C. Weight change measurements and microstructure analysis showed that HF corrosion in polycrystalline ceramics generally occurred at grain boundaries by the dissolution of grain boundary phases although the bulk single crystal may inherently resist attack. Virtually all commercially prepared polycrystalline oxide ceramics (i.e., Al₂O₃, TiO₂, ZrO₂) and nonoxide ceramics (i.e., Si₃N₄, AlN, BN) were extensively corroded while polycrystalline pure carbides (i.e., SiC, TiC, B₄C, WC) resisted corrosion. Equilibrium thermodynamic calculations show that these materials are soluble in HF; however, the kinetics of dissolution are slow enough in some cases to permit useful engineering lifetimes.     

Oxidation of ZrB2–SiC: Influence of SiC Content on Solid and Liquid Oxide Phase Formation

The effect of SiC concentration on the liquid and solid oxide phases formed during oxidation of ZrB₂–SiC composites is investigated. Oxide-scale features called convection cells are formed from liquid and solid oxide reaction products upon oxidation of the ZrB₂–SiC composites. These convection cells form in the outermost borosilicate oxide film of the oxide scale formed on the ZrB₂–SiC during oxidation at high temperatures (≥1500°C). In this study, three ZrB₂–SiC composites with different amounts of SiC were tested at 1550°C for various durations of time to study the effect of the SiC concentration particularly on the formation of the convection cell features. A calculated ternary phase diagram of a ZrO₂–SiO₂–B₂O₃ (BSZ) system was used for interpretation of the results. The convection cells formed during oxidation were fewer and less uniformly distributed for composites with a higher SiC concentration. This is because the convection cells are formed from ZrO₂ precipitates from a BSZ oxide liquid that forms upon oxidation of the composite at 1550°C. Higher SiC-containing composites will have less dissolved ZrO₂ because they have less B₂O₃, which results in a smaller amount of precipitated ZrO₂ and consequently fewer convection cells.     

Hot Hardness of Selected Borides, Oxides, and Carbides to 1900°C

The hot hardness of TiB₂, W₂B₅, ZrB₂, HfB₂, ZrO₂, Al₂O₃, NbC, Tic, TaC_{1- x} , HfG_{1+ x} , (Ta_0.8Hf_0.2)C_{1+ x} , W₂C, and (W_0.65Cr_0.14Re_0.14Ta_0.07)₂C of <95% density was determined to temperatures approaching 1900°C. In all cases, the hardness decreased rapidly with increasing temperature. The data are compared to those available in the literature.     

In Situ TiC/TiB2 Particulate Locally Reinforced Steel Matrix Composites Fabricated Via the SHS Reaction of Ni–Ti–B4C System

The composites synthesized with three kinds of B₄C particles mainly consist of TiC, TiB₂, and the alloy austenite containing Ni element. Ceramic particulate sizes in the composites synthesized with ∼3.5 and ∼45 μm B₄C particles are larger than that synthesized with ∼140 μm B₄C particle. No pores are found between the reinforcing region and matrix in the composites synthesized with ∼3.5 and ∼45 μm B₄C particles, while some large pores exist in the composites synthesized with ∼140 μm B₄C particle. With the decrease of B₄C particle size, the pores in the composites become fewer and the hardness and wear resistance of the composites increase.     

Fabrication and Microstructure Characterization of Ti3SiC2 Synthesized from Ti/Si/2TiC Powders Using the Pulse Discharge Sintering (PDS) Technique

Ti/Si/2TiC powders were prepared using a mixture method (M) and a mechanical alloying (MA) method to fabricate Ti₃SiC₂ at 1200°–1400°C using a pulse discharge sintering (PDS) technique. The results showed that the Ti₃SiC₂ samples with <5 wt% TiC could be rapidly synthesized from the M powders; however, the TiC content was always >18 wt% in the MA samples. Further sintering of the M powder showed that the purity of Ti₃SiC₂ could be improved to >97 wt% at 1250°–1300°C, which is ∼200°–300°C lower than that of sintered Ti/Si/C and Ti/SiC/C powders using the hot isostatic pressing (HIPing) technique. The microstructure of Ti₃SiC₂ also could be controlled using three types of powders, i.e., fine, coarse, or duplex-grained, within the sintering temperature range. In comparison with Ti/Si/C and Ti/SiC/C mixture powders, it has been suggested that high-purity Ti₃SiC₂ could be rapidly synthesized by sintering the Ti/Si/TiC powder mixture at relatively lower temperature using the PDS technique.