Synthesis of titanium diboride TiB2 and Ti-Al-B metal matrix composites

Titanium diboride TiB₂ and TiAl aluminide composites reinforced with in situ borites have been synthesized from the elemental powders of Ti and B, and Ti, Al and B respectively using mechanical alloying technique. No progressive diffusion between Ti and B was observed. The formation of TiB₂ was found to be governed by strong and fast exothermic heat release. This indicates that the formation of TiB₂ compound in local area of mechanically alloyed powder generated high energy which in turn ignited and promoted the formation of new compound in the rest of the area. Because of the presence of Al in Ti-Al-B system, the concentration of Ti or B was diluted. The exothermic reaction between Ti and B was consequently delayed. However, grain refinement of Ti and Al in this system down to nanometer scale is faster than that in Ti-Al system due to the contribution of B. Using X-ray analysis, strong but broad TiAl, and weak TiB and TiB₂ peaks had been detected at 50 h of mechanical alloying indicating the formation of nano TiAl composite reinforced by TiB and TiB₂. However, TiB was, however, not a stable phase; it later was transformed into equilibrium phase of TiB₂ after annealing at 800 °C.     

Reaction-sintered hot-pressed TiAl

Titanium aluminide intermetallic alloys and composites were formed from elemental titanium and aluminium powders by self propagating, high-temperature synthesis in an induction-heated hot-press. The crystal phases, density, transverse rupture stress, and hardness of the reaction-sintered compacts, were observed to be controlled by hot-pressing conditions. The principal phase formed was TiAl together with a significant second-phase concentration of Ti₃AI. The transverse rupture strength (TRS) of the intermetallic composites was observed to vary directly with compact density. Under selected high-temperature synthesis hot-pressing conditions, TRS values were comparable to those obtained for fully dense TiAl. Titanium aluminide composites were formed by adding boron, carbon, silicon and Al₂O₃, and SiC powders and whiskers to the Ti-Al powders before reaction sintering. Changing the alloying additions did not have as strong an effect on properties of the composite compacts as did varying hot-pressing conditions.     

Microstructure and oxidation behaviour of TiAl(Nb)/Ti<Subscript>2</Subscript>AlC composites fabricated by mechanical alloying and hot pressing

TiAl-based intermetallic matrix composites with dispersed Ti₂AlC particles and different amounts of Nb were successfully synthesized by mechanical alloying and hot pressing. The phase evolution of Ti–48 at%. Al elemental powder mixture milled for different times with hexane as a process control agent was investigated. It was found that after milling for 25 h, a Ti(Al) solid solution was formed; also with increase in the milling time to 50 h, an amorphous phase was detected. Formation of a supersaturated Ti(Al) solid solution after 75 h milling was achieved by crystallization of amorphous phase. Addition of Nb to system also exhibited a supersaturated Ti(Al,Nb) solid solution after milling for 75 h, implying that the Al and Nb elements were dissolved in the Ti lattice in a non-equilibrium state. Annealing of 75 h milled powders resulted in the formation of equilibrium TiAl intermetallic with Ti₂AlC phases that showed the carbon that originates from hexane, participated in the reaction to form Ti₂AlC during heating. Consolidation of milled powder with different amounts of Nb was performed by hot pressing at 1000°C for 1 h. Only the presence of γ-TiAl and Ti₂AlC was detected and no secondary phases were observed on the base of Nb. Displacement of γ-TiAl peaks with Nb addition implied that the Nb element was dissolved into TiAl matrix in the form of solid solution, causing the lattice tetragonality of TiAl to increase slightly. The values for density and porosity of samples indicated that condition of hot pressing process with temperature and pressure was adequate to consolidate almost fully densified samples. The isothermal oxidation test was carried out at 1000°C in air to assess the effect of Nb addition on the oxidation behaviour of TiAl/Ti₂AlC composites. The oxidation resistance of composites was improved with the increase in the Nb content due to the suppression of TiO₂ growth, the formation and stabilization of nitride in the oxide scale and better scale spallation resistance.     

Microstructural characteristics and evolution of Ti2AlN/TiAl composites with a network reinforcement architecture during reaction hot pressing process

The microstructural evolution of TiAl matrix composites with a novel network distribution of Ti₂AlN particle reinforcement was studied. The composites were synthesized by reaction hot pressing method using pure Al and nitrided Ti powders as initial materials. Pure Ti powders nitrided at 600 °C for a certain time in an atmosphere of flowing nitrogen turned into new compound Ti(N) powders, which have a shell of titanium nitrides (such as TiN, Ti₂N and TiN_0.3) and a core of Ti–N solid solution. Within the composites synthesized, Ti₂AlN particles, produced by in situ reaction, exhibit a network distribution. The special shell/core structure of the compound Ti(N) powders contributes to this architecture. Nitriding time of the Ti powders greatly affects the microstructure of the composites. Increasing the nitriding time is beneficial to the distribution of Ti₂AlN particles in a continuous network form. However, too long nitriding time can result in the aggregation of Ti₂AlN particles and thus destroy the uniformity of the network structure. The in-situ synthesized Ti₂AlN/TiAl composites with uniform network structure have a superior mechanical property, and their compressive strengths at 800 °C and 1000 °C are 1112 MPa and 687 MPa, respectively.     

Synthesis and microstructure of layered-ternary Ti2AlC ceramic by high energy milling and hot pressing

Fully dense and single-phase Ti₂AlC ceramic was successfully synthesized by a high energy milling and hot pressing using Ti, C and Al as starting materials. The effects of composition of the initial elemental powders and sintering temperatures on the purity and formation of Ti₂AlC were examined. The formation mechanism for the single-phase Ti₂AlC ceramics was investigated by XRD in details, which could be described as follows: the most of initial elements reacted to form TiC and Ti–Al intermetallics; the intermetallics and the residual Ti and Al transformed to TiAl phase; and finally the TiAl intermetallics and the TiC reacted to yield Ti₂AlC.     

Reaction synthesis of titanium aluminides

The formation of titanium aluminides from the elemental powders has been investigated. A traditional powder metallurgy route of compaction (by cold isostatic pressing, hot pressing or hot extrusion) followed by heat treatment was compared with the novel technique of hot extrusion reaction synthesis (HERS). The products from these different production methods were characterised by x-ray diffraction and microscopy (light and scanning electron). The intermetallic compound formed under most processing conditions wasTiAl₃. Only when there was a rapid increase in temperature to high temperatures, as found in induction heating of compacts or in HERS, were the compounds Ti₃Al and TiAl formed.     

Titanium aluminides from cold-extruded elemental powders with Al-contents of 25–75 at% Al

Titanium aluminide alloys were prepared from cold-extruded elemental Ti and Al powders with compositions ranging from 25 to 75 at % Al. The production route in this study includes four essential steps: mixing, precompaction, cold-extrusion and reaction treatment. During reaction treatment, the intermetallic phases Ti₃Al, TiAl and TiAl₃ are formed by interdiffusion of Ti and Al, and pore formation takes place because of the different diffusivities of Ti and Al. The processes of phase formation, as well as pore formation, were studied by means of calorimetric, dilatometric and metallographic methods. In order to obtain nearly fully dense specimens, the technique of hot isostatic pressing was applied. The sintering behaviour and microstructures of the prepared alloys are reported.     

Processing and Characterization of In Situ (TiC–TiB2)p/AZ91D Magnesium Matrix Composites

In this paper, a practical and cost‐effective processing route, in situ reactive infiltration technique, was utilized to fabricate magnesium matrix composites reinforced with a network of TiC–TiB₂ particulates. These ceramic reinforcement phases were synthesized in situ from Ti and B₄C powders without any addition of a third metal powder such as Al. The molten Mg alloy infiltrates the preform of (Ti_p + B₄C_p) by capillary forces. The microstructure of the composites was investigated using scanning electron microscope (SEM)/energy dispersive X‐ray spectroscopy (EDS). The compression behavior of the composites processed at different conditions was investigated. Also, the flexural strength behavior was assessed through the four‐point‐bending test at room temperature. Microstructural characterization of the (TiB₂–TiC)/AZ91D composite processed at 900 °C for 1.5 h shows a relatively uniform distribution of TiB₂ and TiC particulates in the matrix material resulting in the highest compressive strength and Young's modulus. Compared with those of the unreinforced AZ91D Mg alloy, the elastic modulus, flexural and compressive strengths of the composite are greatly improved. In contrast, the ductility is lower than that of the unreinforced AZ91D Mg alloy. However, this lower ductility was improved by the addition of MgH₂ powder in the preform. Secondary scanning electron microscopy was used to investigate the fracture surfaces after the flexural strength test. The composites show signs of mixed fracture; cleavage regions and some dimpling. In addition, microcracks observed in the matrix show that the failure might have initiated in the matrix rather than from the reinforcing particulates.     

Production of titanium particulate metal matrix composite by mechanical milling

Abstract

Mechanical milling is an established production method for aluminium particulate metal matrix composites (MMCs). There are examples of its use for high performance automotive applications and within the aerospace industry. The production of a titanium particulate MMC is still in the developmental stage. However, compared to conventional titanium alloys such materials offer improvements in stiffness, strength, fatigue and creep properties, high temperature capability, and wear resistance. This paper describes the use of mechanical milling for the production of titanium particulate MMCs with the addition of 10 vol.-%TiB. Gas atomised titanium powders with additions of either boron or TiB₂ were milled in a high purity argon atmosphere to avoid contamination of the powders by oxygen or nitrogen. The distribution of the boron or TiB₂ with increasing milling time is discussed along with the effect of the alloy composition. Gas atomised, hydride dehydride, and sponge fine powder blends are also compared. The powders were subsequently hot isostatically pressed at 500°C for 2 h at 150 MPa followed by 900°C for 2 h at 150 MPa. During this consolidation process TiB was formed by an in situ reaction between either the TiB₂ or boron and the titanium matrix.     

Fabrication of multilayered titanium aluminide sheets by self-propagating high-temperature synthesis reaction using hot rolling and heat treatment

This study is concerned with the fabrication of multilayered and bulk Ti aluminide sheets by self-propagating high-temperature synthesis (SHS) reaction using hot rolling and heat treatment. A multilayered Ti/Al sheet was prepared by stacking thin Ti and Al sheets alternatively. When this sheet was hot-rolled and heat-treated at 1000°C, a multilayered sheet composed of Ti₃Al and TiAl was made through the process of formation and growth of intermetallic phases at Ti/Al interfaces and porosity reduction. A bulk Ti aluminide sheet having a lamellar structure of TiAl and Ti₃Al was also fabricated successfully by heat treatment at 1400°C.     

Property-microstructure correlation in in situ formed Al2O3, TiB2 and Al3Ti mixture-reinforced aluminium composites

The in situ formed Al₂O₃, TiB₂ and Al₃Ti mixture-reinforced aluminium composites were successfully fabricated by the reaction sintering of the TiO₂-B-Al system in a vacuum. With increasing boron content in the TiO₂-B-Al system, the amount of generated TiB₂ in the composites increased and Al₃Ti content decreased. At the same time the distribution uniformity of the in situ formed Al₂O₃ and TiB₂ particulates was obviously improved, and the size of the Al₃Ti particles was reduced. The in situ Al₂O₃ and TiB₂ particulates had sizes from 0.096–1.88 m. The interface between the in situ formed particulates and the aluminium matrix was clean, and no consistent crystallographic orientation relationship was found. The strength and elastic modulus of the composites was significantly improved by lowering the Al₃Ti content. When the boron content in the TiO₂-B-Al system rose, the morphology of the tensile fracture surface of the composites was changed from large fractured Al₃Ti blocks and fine dimples, to fine dimples and pulled-out particulates. The strengthening and fracture of the composites have been modelled.     

The effects of boron in TiAl/Ti3Al

The TiAl/Ti₃Al interfacial misfit dislocations structures were investigated by TEM in Ti-45Al alloy and Ti-45Al/TiB₂ composite. For TiAl with c/a = 1.02, only a single set of misfit dislocation arrays are crystallographically possible; these were observed in Ti-45Al alloy. However, the observation of three sets of misfit dislocation arrays in the Ti-45Al/TiB₂ composite suggests that the occupation of octahedral sites in the TiAl structure by excess boron was responsible for a decrease in the c/a ratio leading to an increased fcc character of the TiAl at the TiAl/Ti₃Al interface.     

Sintering behavior of mechanically alloyed Ti-48Al-2Nb aluminides

Ti-Al intermetallics have been produced using mechanical alloying technique. A composition of Ti-48Al-2Nb at % powders was mechanically alloyed for various durations of 20, 40, 60, 80 and 100 h. At the early stages of milling, a Ti (Al) solid solution is formed, on further milling the formation of amorphous phase occurs. Traces of TiAl and Ti₃Al were formed with major Ti and Al phases after milling at 40 h and beyond. When further milled, phases of intermetallic compounds like TiAl and Ti₃Al were formed after 80 hours of milling and they also found in 100 h milled powders. The powders milled for different durations were sintered at 785°C in vacuum. The mechanically alloyed powders as well as the sintered compacts were characterized by XRD, FESEM and DTA to determine the phases, crystallite size, microstructures and the influence of sintering over mechanical alloying.     

Mechanical response of reaction phases of the TiAl/steel brazed joint under a tensile load

This article offers a study of a mechanical response of the TiAl/Steel brazed joint. The (i) intermetallic reaction layer’s phases, (ii) the residue filler, and the (iii) base metals constitute the complex structure considered. The study features TiAl and 42CrMo steel brazed with an AgCuTi filler metal. The analysis includes the microstructural study and an evaluation of mechanical properties of the brazed joint. In addition, the fracture behavior of the joint under a tensile loading in situ is studied in the context of the impact that reaction phases may have on the joint properties. The results of the study indicate that the complex joint structure is due to the presence of a ternary intermetallic reaction layer, as well as the presence of intermetallics in the filler residue. The multilayered structure includes Ti₃Al+AlCuTi+AlCu₂Ti ternary intermetallic reaction layer, Ag(Cu) residue filler, AlCu₂Ti intermetallic dispersed in the residue braze and TiC layer. The hardness sequence of the structure has been established. The crack initiation, its propagation, and an ultimate fracture are associated primarily with Ti₃Al+AlCuTi+AlCu₂Ti ternary intermetalics layer.     

Preparation of titanium diboride powders from titanium alkoxide and boron carbide powder

Titanium diboride powders were prepared through a sol-gel and boron carbide reduction route by using TTIP and B₄C as titanium and boron sources. The influence of TTIP concentration, reaction temperature and molar ratio of precursors on the synthesis of titanium diboride was investigated. Three different concentrations of TTIP solution, 0.033/0.05/0.1, were prepared and the molar ratio of B₄C to TTIP varied from 1.3 to 2.5. The results indicated that as the TTIP concentration had an important role in gel formation, the reaction temperature and B₄C to TTIP molar ratio showed obvious effects on the formation of TiB₂. Pure TiB₂ was prepared using molar composition of Ti: B₄C = 1: 2.3 and the optimum synthesis temperature was 1200°C.     

Effect of Nb2O5 on the microstructure and mechanical properties of TiAl based composites produced by hot pressing

In situ composites of TiAl reinforced with Al₂O₃ particles are successfully synthesized from an elemental powder mixture of Ti, Al and Nb₂O₅ by the hot-press-assisted reaction synthesis (HPRS) method. The as-prepared composites are mainly composed of TiAl, Al₂O₃, NbAl₃, as well as small amounts of the Ti₃Al phase. The in situ formed fine Al₂O₃ particles tend to disperse on the matrix grain boundaries of TiAl resulting in an excellent combination of matrix grain refinement and uniform Al₂O₃ distribution in the composites. The Rockwell hardness and densities of TiAl based composites increase gradually with increasing Nb₂O₅ content, and the flexural strength and fracture toughness of the composites have the maximum values of 634 MPa and 9.78 MPa m^1/2, respectively, when the Nb₂O₅ content reaches 6.62 wt.%. The strengthening mechanism was also discussed.     

Thermal conductivities of Ti-SiC and Ti-TiB2 particulate composites

Composites of commercial-purity titanium reinforced with 10 and 20 vol % of SiC and TiB₂ particulates were produced by powder blending and extrusion. Heat treatments were conducted on each of these composites. The thermal diffusivities of the composites were measured as a function of temperature using the laser flash technique. Thermal conductivities were inferred from these measurements, using a rule-of-mixtures assumption for the specific heats. It has been shown that, while an enhancement of the thermal conductivity is expected to arise from the presence of both types of reinforcement, this behaviour is in fact observed only with the Ti-TiB₂ composites. The thermal conductivity of Ti-TiB₂ composites is significantly greater than that of the unreinforced matrix and rises with increasing volume fraction of reinforcement. In contrast, the conductivities of the Ti-SiC composites were considerably lower than that of the unreinforced titanium and decreased with increasing volume fraction of SiC reinforcement. These results have been interpreted in terms of the thermal resistance of the reaction layers which exist between the matrix and two types of particulate reinforcements. The faster reaction kinetics between SiC and Ti gives rise to a thicker reaction layer for a given heat treatment than that between Ti and TiB₂ and is also accompanied by a much larger volume change (– 4.6%). It is proposed that this volume decrease, giving rise to interfacial damage and a network of microcracks, is at least partly responsible for a high interfacial thermal resistance, reducing the conductivity of the Ti-SiC composite. These results indicate that TiB₂ would be preferable to SiC as a reinforcement in Ti for situations where a high thermal conductivity would be beneficial.     

Fabrication of TiB2/TiC composites by the directional reaction of titanium with boron carbide

Dense TiB₂/TiC composites were fabricated by the directional reaction of molten titanium with boron carbide preform. The reaction between pure molten titanium and boron carbide preform could not progress due to reaction choking. However, when a few weight per cent of nickel were added in the titanium, the reaction progressed continuously and resulted in TiB₂/TiC composites. A gradient of grain sizes was observed in the reaction products. The processing temperature affected the microstructure of the reaction products rather than the reaction rate. The degree of grain-size gradient in the reaction product increased with the processing temperature.     

Laser-induced vapour-phase syntheses of boron and titanium diboride powders

Small diameter boron and titanium diboride powders were synthesized from vapour phase reactants heated with infrared radiation from a CO₂ laser. Boron powders were synthesized from BCI₃ + H₂ gas mixtures undfrom B₂H₆. TiCl₄ + B₂H₆ gas mixtures yielded TiB₂ powder. BCI₃ + H₂ + TiCl₄ gas mixtures yielded TiCl₂ powder but no TiB₂. Novel equipment designed to vapourize TiCI₄ liquid is described, Detailed characterizations of the product powders are presented.     

Interface kinetics of combustion–diffusion bonding of Ni3Al/Ni and TiAl/Ti under direct current field

The bonding of TiB₂–Ni and TiC–Ni composites to, respectively, Ni and Ti substrates was investigated by field-activated and pressure-assisted synthesis. Bonding and in situ synthesis was utilized to prepare (TiB₂)_pNi/Ni₃Al/Ni (Composition 1) and (TiC)_pNi/TiAl/Ti (Composition 2) joining structures. The effect of applied current on the kinetics of formation of the diffusion layer between the substrate (Ni or Ti) and the respective intermetallic layer (Ni₃Al or TiAl) was investigated. For both compositions, the current was shown to have a marked influence of the activation energy of formation of the layer, decreasing it by as much as 31 %. Calculations of adiabatic temperatures suggest a possible current contribution to interdiffusion, as has been reported previously.