Processing and Properties of TiB2 with MoSi2 Sinter-additive: A First Report

The densification of non-oxide ceramics like titanium boride (TiB₂) has always been a major challenge. The use of metallic binders to obtain a high density in liquid phase-sintered borides is investigated and reported. However, a non-metallic sintering additive needs to be used to obtain dense borides for high-temperature applications. This contribution, for the first time, reports the sintering, microstructure, and properties of TiB₂ materials densified using a MoSi₂ sinter-additive. The densification experiments were carried out using a hot-pressing and pressureless sintering route. The binderless densification of monolithic TiB₂ to 98% theoretical density with 2–5 μm grain size was achieved by hot pressing at 1800°C for 1 h in vacuum. The addition of 10–20 wt% MoSi₂ enables us to achieve 97%–99%ρ_th in the composites at 1700°C under similar hot-pressing conditions. The densification mechanism is dominated by liquid-phase sintering in the presence of TiSi₂. In the pressureless sintering route, a maximum of 90%ρ_th is achieved after sintering at 1900°C for 2 h in an (Ar+H₂) atmosphere. The hot-pressed TiB₂–10 wt% MoSi₂ composites exhibit high Vickers hardness (∼26–27 GPa) and modest indentation toughness (∼4–5 MPa·m^1/2).     

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.     

The Effect of Surface Oxides During Hot Pressing of TiB2

Hot pressing of TiB₂ has been investigated with particular emphasis on the evolution of secondary phases originating from the initial surface oxide layer on the TiB₂ powders. Carbothermal reduction of the surface oxides during sintering was also investigated by adding carbon to the TiB₂ powder. TiO_{1− x} C _x was shown to be the main secondary phase in hot-pressed TiB₂, and carbon was shown to strongly influence on sintering process and the amount, composition and distribution of the secondary phase TiO_{1− x} C _x . The formation of TiO_{1− x} C _x is discussed in relation to volatile boron oxide, which reacts with the graphite die to produce CO gas, which further may cause transport of carbon into TiB₂ during sintering before pore closure. Finally it was demonstrated that the density could be controlled by addition of carbon to the TiB₂ powder.     

Simultaneous Spark Plasma Synthesis and Densification of TiC–TiB2 Composites

The simultaneous synthesis and densification of dense TiC–TiB₂ composite has been investigated starting from Ti, B₄C, and C as reactants, and using the spark plasma sintering (SPS) technique. The optimal conditions for complete conversion of the reactants to the composite were determined for different applied DC current levels. A kinetic investigation performed allows us to conclude that solid-state diffusion is the mechanism governing the synthesis process. It is seen that TiC is the first phase formed, while TiB₂ formation occurs afterward. Two intermediate boride phases, i.e. TiB and Ti₃B₄, are also formed but, as the SPS holding time was augmented, they were gradually and completely converted to TiB₂. Moreover, it is found that in order to reach relatively high dense products, an electric current needs to be applied for time intervals longer than those required for obtaining complete conversion. A pure dense product (relative density ∼98%) was obtained when an electric pulsed current of 1100 A and a mechanical pressure of 20 MPa were applied for about 4 min.     

Densification, Sintering Reactions, and Properties of Titanium Diboride With Titanium Disilicide as a Sintering Aid

In the present investigation, we explore the feasibility of using TiSi₂ as a sintering aid to densify titanium diboride (TiB₂) at a lower sintering temperature (<1700°C). The hot-pressing experiments were conducted in the temperature range of 1400°–1650°C for 1 h in an argon atmosphere and TiSi₂ addition to TiB₂ was restricted up to 10 wt%, with an overall objective to densify the materials with a fine microstructure as well as to assess the feasibility of enhancing the mechanical and electrical properties. When all the materials were hot pressed at 1650°C, the hot-pressed TiB₂– X % TiSi₂ ( X =0, 2.5, 5, 10 wt%) composites were found to be densified to more than 98%ρ_th (theoretical density), except monolithic TiB₂ (∼94%ρ_th). An interesting observation is the formation of a Ti₅Si₃ phase and this phase formation is described by thermodynamically feasible sintering reactions. Our experimental results suggest that the optimal TiB₂–5 wt% TiSi₂ composite can exhibit an excellent combination of properties, including a high hardness of 25 GPa, an elastic modulus of 518 GPa, an indentation toughness of ∼6 MPa·m^1/2, a four-point flexural strength of more than 400 MPa, and an electrical resistivity of 10 μΩ·cm.     

Factors Affecting the Porosity and Bending Strength of Ti(CN)-TiB2 Materials

This paper describes the effects that the particle size of Ti(CN) and TiB₂ powder, oxygen content of the TiB₂ powder, and Co impurity content in the starting raw materials have on the porosity and bending strength ofTi(CN)-30% TiB₂ materials obtained by ordinary sintering.     

Ablation-Resistance of Combustion Synthesized TiB2–Cu Cermet

TiB₂–Cu ceramic–metal composites were prepared by combustion synthesis of elemental titanium, boron, and copper powders. The synthesized product consisted of two phases: TiB₂ and copper. The addition of copper improved the strength and fracture toughness, thermal expansion coefficient, and thermal conductivity of TiB₂. Thermal shock and ablation resistances of TiB₂–Cu composites were studied using a plasma torch arc heater. Monolithic TiB₂ failed catastrophically when the plasma arc flow reached the specimen surface. However, no cracks were found on the ablation surface of the TiB₂–Cu ceramic–metal composites. The fractional mass loss was 4.09% for a TiB₂–40Cu composite, which was close to the traditional W/Cu alloys. Volatilization of metal binder and mechanical erosion of TiB₂ were observed to be the major ablation mechanisms. An ablation process model is proposed for the TiB₂–Cu composites.     

Densification and Mechanical Properties of Titanium Diboride with Silicon Nitride as a Sintering Aid

Titanium diboride (TiB₂) was hot-pressed at a temperature of 1800°C, and silicon nitride (Si₃N₄) was added as a sintering aid. The amount of Si₃N₄ that was added had a significant influence on the sinterability and mechanical properties of the TiB₂. When a small amount (2.5 wt%) of Si₃N₄ was added, the Si₃N₄ reacted with titania (TiO₂) that was present on the surface of the TiB₂ powder to form titanium nitride (TiN), boron nitride (BN), and amorphous silica (SiO₂). The elimination of TiO₂ suppressed the grain growth effectively, which led to an improvement in the densification of TiB₂. The formation of SiO₂ also was deemed beneficial for densification. The mechanical properties-especially, the flexural strength-were enhanced remarkably through these improvements in the sinterability and microstructure. On the other hand, when a large amount (greaterthan equal to5 wt%) of Si₃N₄ was added, the mechanical properties were not improved much, presumably because of the extensive formation of a glassy Si-Ti-O-N phase at the grain boundaries.     

Acid Leaching of SHS Produced Magnesium Oxide/Titanium Diboride

The stoichiometric self-propagating high-temperature synthesis (SHS) thermite reaction involving magnesium (Mg), titanium dioxide (TiO₂), and boron oxide (B₂O₃) forms MgO and titanium diboride (TiB₂) as final products. Selective acid leaching is used to remove the MgO leaving TiB₂ powder. This study investigates the acid leaching of SHS-produced MgO/TiB₂ powders and a stoichiometric mixture of commercially obtained MgO and TiB₂ powders. Leaching was conducted at pH levels of 4.0, 2.5, and 1.0 by the introduction of concentrated aliquots of HNO₃. This method maintains a minimum pH target throughout the leaching process, thereby sustaining a dynamic concentration to remove the oxide. The optimal leaching conditions were determined to be at 90°C at a minimum pH target of 2.5 for the SHS-produced product. At these conditions, conversion percentages of 83%–84% of MgO were measured with only trace amounts of TiB₂ measured in the solution (<100 μg/L). Conversion percentages for each leaching condition and dissolution mass of solid MgO and TiB₂ at each pH are also reported. Results from powder X-ray diffraction confirm the removal of MgO and minimal dissolution of TiB₂, and indicate the formation of unidentified compounds. Inductively coupled plasma mass spectrometry (ICP) was used to analyze the ionic composition and extent of leaching. Scanning electron microscopy was used to observe the particle morphology of the leached powders.     

Mechanical Properties of Hot-Pressed TiB2-ZrO2 Composites

The use of monoclinic ZrO₂ as an additive improves the mechanical properties of TiB₂-based composites without the use of stabilizers. In particular, TiB₂-30% ZrO₂ compacts exhibited a transverse rupture strength of 800 MN/m², few pores, and a K_{I c} of 5 MPa·m^1/2. The high strength and toughness are thought to result mainly from the presence of partially stabilized tetragonal ZrO₂ and from solid solution of (TiZr)B₂ formed in sintering.     

Combustion Synthesis/Dynamic Densification of a TiB2-SiC Composite

The Ti + 2B exothermic chemical reaction was used in combination with a high-velocity forging step to produce dense TiB₂-(20 vol%)SiC composites. Densities in excess of 96 % of the theoretical were achieved for both SiC particulate and fiber additions. X-ray diffractometry revealed the products of the reaction to be TiB₂ and SiC. The microstructures are composed of spheroidal TiB₂ phase, a highly contiguous SiC binder phase, and an apparent eutectic between TiB₂ and SiC located at regions of preexisting SiC additions. These microstructural features suggest that SiC underwent a peritectic phase transformation. Thermodynamic analysis predicts that at least 41 vol% SiC addition is needed to prevent the loss of the starting morphologies by the peritectic reaction.     

Electrochemical Chromium(III) Oxide Coatings on Non-oxide Ceramic Substrates

SiC and TiB₂ were electrochemically coated with Cr₂O₃ from a 0.1 M aqueous solution of chromium nitrate hydrate with ethanol additives. On both substrate materials poly-crystalline Cr₂O₃ was formed at current densities from 5 to 50 mA/cm² and deposition durations of 5 to 30 min. The coating weight increased with current density and with deposition time. The as-deposited coatings contained microcracks due to drying shrinkage. Microstructural observations indicate that sintering of the Cr₂O₃ coatings on TiB₂ at 1100°C for 1 n in a reducing atmosphere in a closed graphite crucible causes the densification of the coating via a liquid phase, which forms by oxidation of TiB₂. Under similar conditions, the Cr₂O₃ coatings on SiC may be sintered via an evaporation–condensation mechanism.     

Role of Microstructure and Intergranular Phases in Stress Corrosion of TiB2 Exposed to Liquid Aluminum

The resistance of several polycrystalline TiB₂ materials to penetration by liquid aluminum at 970°C was investigated, and their microstructures were characterized. The grain-boundary properties of individual diborides rather than the intrinsic properties of TiB₂ are thought to control stress corrosion susceptibility in liquid metal environments.     

Sintering of in-Situ Synthesized Sic–TiB2 Composites with Improved Fracture Toughness

TiB₂-particle reinforcement is one of the most successful methods for improving the fracture toughness of SiC ceramics.^1–3 Commercially available TiB₂ powders, however, have a large particle size and/or are highly reactive so that they are not favorable as a starting powder. In the present work, TiB₂ particles are formed by an in situ reaction between TiC and boron. The reaction takes place during sintering between 1000° and 1600°C and is accompanied by a large volume expansion. Under optimum conditions, dense composites (> 98% of theoretical) can be obtained by pressureless sintering using B and C as sintering additives. The in situ reaction method enables, for the first time, a complete densification of SiC-particulate composites by pressureless sintering. The fracture toughness of the composites was approximately 30% higher than that of the monolithic SiC ceramic.     

Chemical Vapor Infiltration of TiB2-Matrix Composites

The efficiency of the Hall–Heroult electrolytic reduction of aluminum can be substantially improved by the use of a TiB₂ cathode. The use of TiB₂ components, however, has been hampered by the brittle nature of the material and the grain boundary attack of sintering-aid phases by molten aluminum. In the current work, TiB₂ is toughened through the use of reinforcing fibers, with chemical vapor infiltration used to produce the TiB₂ matrix. In early efforts it was observed that the formation of TiB₂ from chloride precursors at fabrication temperatures below 900–1000°C may have allowed the retention of destructive levels of chlorine. At higher fabrication temperatures (>1000°C), using appropriate infiltration conditions as determined from the use of a process model, TiB₂/THORNEL P-25 fiber composites have been fabricated in 20 h. The improved composite material has been demonstrated to be stable in molten aluminum in short-duration (24 h) tests.     

Elastic Properties and Microcracking Behavior of Particulate Titanium Diboride–Silicon Carbide Composites

The spontaneous microcracking of particulate TiB₂–SiC composites is studied as a function of TiB₂ volume fraction. The degree of microcracking was examined by measuring elastic properties from room temperature to 1300°C. The results showed that only one composition contains microcracks. All other compositions did not microcrack regardless of TiB₂ volume fraction. This was attributed to the difference in the sintering aids. In particular, the Al₂O₃ sintering aid needed in these compositions had reacted with SiO₂ to form an amorphous grain boundary phase that allowed residual stresses to relax by viscous flow at moderate to high temperatures. The existence of this amorphous grain boundary phase was directly observed by transmission electron microscopy.     

Preferential Grain Orientation in Hot Pressed TiB2

Preferential grain growth is reported for hot pressed titanium diboride (TiB₂) prepared at 1800°C and 50 MPa. Orientation imaging microscopy and X-ray diffraction revealed that the grains in the material were preferentially orientated with the [001] direction parallel to the mechanical field. The experimental findings are discussed, with emphasis on the anisotropic properties of TiB₂.     

Influence of MoSi2 Addition on Load-Dependent Fretting Wear Properties of TiB2 Against Cemented Carbide

In an earlier work, it was observed that the use of MoSi₂ (up to 10 wt%) enhanced the densification and mechanical properties of TiB₂. Therefore, the motivation of this study is three-fold: (a) to assess whether a small amount of MoSi₂ addition can enhance wear resistance property, (b) to study whether the MoSi₂ addition will influence the formation of a tribochemical layer, and (c) to correlate the wear resistance with material properties in TiB₂–MoSi₂ materials. In order to address these issues, a series of fretting experiments were conducted systematically by varying load (2, 5, and 10 N) at an oscillating frequency of 4 Hz and a 100 μm linear stroke, for a duration of 100 000 cycles with a cemented carbide (WC—6 wt% Co cermet) ball as a counterbody. The average coefficient of friction of the TiB₂ samples varied within a narrow range (0.50–0.54), without being much affected by either the sintering additive or the load. The wear volume increased with increasing load, while the specific wear rate of all the TiB₂ compositions falls within a mild wear regime (1.1–3.4 × 10⁻⁶ mm³/Nm). Based on the experimental results, it can be said that the addition of MoSi₂ degrades neither the wear resistance properties nor the frictional properties of TiB₂, within the investigated load regime. The microcracking-induced spalling has been found to be the dominant mechanism and, consequently, the wear volume is observed to have a linear dependency on the abrasion parameter. It is noteworthy that the tribo-oxidation as well as the formation of finer wear debris particles occurs to a limited extent.     

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.     

A New Carbide-Base Cermet Containing Tic, TiB2, and CoSi

A new high-temperature material with excellent stress-sustaining characteristics at 1800°F. has been developed. The weight per cent composition of this Tic-base cermet is 55.4 TIC + 17.9 TiB₂+ 16.7 Co + 10 Si, and the principal phases present after sintering are Tic, TiB₂, and CoSi. The research on and development of this material and some of its physical properties are discussed.