Reaction Scheme and Liquidus Surface of the Ternary System Aluminum-Chromium-Titanium

The constitution of the ternary system Al-Cr-Ti is investigated over the entire composition range using X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), differential thermal analysis (DTA) up to 1500 °C, and metallography. Solid-state phase equilibria at 900 °C are determined for alloys containing ≤75 at. pct aluminum and at 600 °C for alloys containing >75 at. pct Al. A reaction scheme linking these solid-state equilibria with the liquidus surface is presented. The liquidus surface for ≤50 at. pct aluminum is dominated by the primary crystallization field of bcc β(Ti,Cr,Al). In the region >50 at. pct Al, the ternary L1₂-type phase τ forms in a peritectic reaction p _max at 1393 °C from L + TiAl. Furthermore, with the addition of chromium, the binary peritectic L + α(Ti,Al) = TiAl changes into an eutectic L = α(Ti,Al) + TiAl. This eutectic trough descends monotonously through a series of transition reactions and ternary peritectics to end in the binary eutectic L = Cr₇Al₄₅ + (Al).     

Comparison of orthorhombic and alpha-two titanium aluminides as matrices for continuous SiC-reinforced composites

The attributes of an orthorhombic Ti aluminide alloy, Ti-21Al-22Nb (at. pct), and an alpha-two Ti aluminide alloy, Ti-24Al-11Nb (at. pct), for use as a matrix with continuous SiC (SCS-6) fiber reinforcement have been compared. Foil-fiber-foil processing was used to produce both unreinforced (“neat”) and unidirectional “SCS-6” reinforced panels. Microstructure of the Ti-24A1-11Nb matrix consisted of ordered Ti₃Al (α ₂) + disordered beta(β), while the Ti-21 Al-22Nb matrix contained three phases: α₂, ordered beta (β ₀), and ordered orthorhombic(O). Fiber/ matrix interface reaction zone growth kinetics at 982 °C were examined for each composite system. Although both systems exhibited similar interface reaction products(i.e., mixed Ti carbides, silicides, and Ti-Al carbides), growth kinetics in theα ₂ +β matrix composite were much more rapid than in theO +β ₀ +α ₂ matrix composite. Additionally, interfacial reaction in theα ₂ +β} composite resulted in a relatively large brittle matrix zone, depleted of beta phase, which was not present in theO +β ₀+α ₂ matrix composite. Mechanical property measurements included room and elevated temperature tensile, thermal stability, thermal fatigue, thermo-mechanical fatigue (TMF), and creep. The three-phase orthorhombic-based alloy outperformed the α₂+β alloy in all of these mechanical behavioral areas, on both an absolute and a specific(i.e., density corrected) basis.     

Reaction of Ti and Ti-Al alloys with alumina

The reaction of single-crystal Al₂O₃ with pure Ti and Ti-Al alloys with different Al concentrations was examined in the temperature range of 1173 to 1573 K. Significant reaction occurred between A1₂O₃ and the Ti-Al alloys with Al concentrations lower than that corresponding to the γ-TiAl phase. The reaction mechanism was determined to be simultaneous diffusion of Al and atomic oxygen from A1₂O₃ into Ti and the Ti-Al alloys.     

Evolution of boride morphologies in TiAl-B alloys

The solidification of γ-TiAl alloys with relatively low (<2 at. pct) additions of boron is discussed. Binary Ti-Al alloys containing 49 to 52 at. pct Al form primary α-(Ti) dendrites from the melt, which are subsequently surrounded by γ segregate as the system goes through the peritectic reactionL + α →γ. Alloys between 45 and 49 at. pct Al go through a double peritectic cascade, forming primary β-(Ti) surrounded by α-(Ti) and eventually by γ in the interdendritic spaces. Boron additions to these binary alloys do not change the basic solidifi-cation sequence of the matrix but introduce the refractory compound TiB₂ in a variety of mor-phologies. The boride develops as highly convoluted flakes in the leaner alloys, but needles, plates, and equiaxed particles gradually appear as the B content increases above ∼1 at. pct. Increasing the solidification rate initially promotes the formation of flakes over plates/needles and ultimately gives way to very fine equiaxed TiB₂ particles in the interdendritic spaces of the metallic matrix. Furthermore, the primary phase selection in the 49 to 52 at. pct Al range changes from α-(Ti) to β-(Ti) at supercoolings of the order of 200 K. The different boride morphologies are fully characterized, and their evolution is rationalized in terms of differences in their nucleation and growth behavior and their relationship to the solidification of the inter-metallic matrix. Formerly Research Assistant, University of California-Santa Barbara (UCSB) Formerly Professor of Materials and Dean of the College of Engineering at UCSB     

Alloying mechanism of beta stabilizers in a TiAl alloy

The effects of beta stabilizers such as Fe, Cr, V, and Nb on the microstructures and phase constituents of Ti₅₂Al₄₈-xM (x=0, 1.0, 2.0, 4.0, or 6.0 at. pct and M=Fe, Cr, V, and Nb) alloys were studied. The dependence of the tensile properties and creep resistance of TiAl on the alloying elements, especially the formation of B2 phase, was investigated. Fe is the strongest B2 stabilizer, Cr is second, V is an intermediate stabilizer, and Nb is the weakest stabilizer. The composition partitioning of Fe, Cr, V, and Nb in the γ phase is affected by the formation of B2 phase. The peaks of the tensile strengths and creep rupture life of Ti₅₂Al₄₈-xM generally occur at the maximum solid solution of these elements in the γ phase, which is just before the formation of B2 phase. Ti₅₂Al₄₈-0.5Fe shows an attractive elongation of 2.5 pct at room temperature, and the Ti₅₂Al₄₈-1V, Ti₅₂Al₄₈-Cr, and Ti₅₂Al₄₈-2Nb alloys have about 1.1 to 1.3 pct elongation at room temperature. The increase of tensile strengths and creep resistance with increasing Fe, Cr, V, and Nb contents is chiefly attributed to the solid-solution strengthening of these elements in the γ phase. The appearance of B2 phase deteriorates the creep resistance, room-temperature strengths, and ductility. With respect to the maximum solid-solution strengthening, an empirical equation of the Cr equivalent [Cr] is suggested as follows: [Cr]=Cr+Mn+3/5V+3/8Nb+3/2 (W+Mo)+3Fe=1.5 to 3.0. The solid-solution strengthening mechanism of Fe, Cr, V, and Nb at room temperature arises from the increase of the Ti 3s and Al 2s binding energies in Ti-Ti and Al-Al bonds, and the retention of the strength and creep resistance at elevated temperatures in Ti₅₂Al₄₈-xM is mainly attributed to the increase of the Ti 3s and Al 2s binding energies in Ti-Al bonds in γ phase. The decrease of the Ti 3p and Al 2p binding energies in Ti-Ti, Ti-Al, and Al-Al bonds benefits the ductility of TiAl.     

Microstructure evolution in metal-intermetallic laminate (MIL) composites synthesized by reactive foil sintering in air

Metal-intermetallic (aluminide) laminate (MIL) composites have been fabricated in air using dissimilar metal foils. Foils of varying Al thickness were reacted with foils of Ti-3Al-2.5V resulting in microstructures of well-bonded metal-intermetallic layered composites with either Ti or Al residual metal layers alternating with the Al₃Ti intermetallic layers. The MIL composites exhibit a very high degree of microstructural design and control. Microstructure characterization by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), and X-ray diffractometry (XRD) has been performed, and basic physical properties of the Ti-Al composites have been determined. The Ti-Al reaction has been studied by interrupting the reaction processing, in steps, to observe the microstructural changes. An oxide layer between the Ti and Al foils initially controls the reaction kinetics. After breakdown of the oxide layer, a two-phase Al+Al₃Ti layer (∼10 μm thickness) is formed. After formation of the two-phase layer, liquid phases are continuously present, and Al₃Ti spherules (∼10 μm diameter) are formed through interfacial tension, solidify (in times of 2 to 4 μs), and are expelled into the liquid. This mechanism allows for a continuous reaction interface and higher reaction rates. Both reaction regimes, diffusion through the oxide, and, subsequently, the intermetallic phase reaction mechanism result in linear kinetics.     

Evaporation behavior of aluminum during the cold crucible induction skull melting of titanium aluminum alloys

Taking the Ti-Al binary alloy as an example, this article studied the evaporation behavior of Al during the cold crucible induction skull melting (ISM) process of titanium alloys. A formula was deduced to predict the activity of Al in a molten Ti-Al binary system. The calculated activity of Al negatively deviates from an ideal solution. A model was established to judge the evaporation controlling mode and, on this basis, several conclusions were obtained. (1) The evaporation controlling mode of Al in molten Ti-Al transfers from the evaporation reaction controlling mode to the double controlling mode (diffusion and evaporation reaction) with increasing melt temperature (T _ms) and/or Al content (x _Al) and/or decreasing pressure (P) in the melting chamber. (2) The expression P≤P _crit (P _crit≈0.44 P _e(Al)) is a criterion used to judge whether the evaporation is in the state of free evaporation. (3) The term P _impe (P _impe=(3.5 to 4) P _e(Al)) is a critical value which impedes the evaporation loss. Almost all of common used ternary additions could enhance the activity of Al in molten Ti-Al and, accordingly, aggravate the evaporation of Al, except for Zr. The enhancing sequence is Y, Ni, Nb, Mn, V, Fe, Cr, Mo, Cu, Si, W, Mg, B, and Sn. The Al evaporation mass-transfer losses, measured from the melting experiments of several titanium aluminum alloys, were in reasonable agreement with the calculated results.     

Thermodynamics of calcium and oxygen in molten titanium and titanium-aluminum alloy

The deoxidation equilibrium of molten titanium and titanium-aluminum alloys saturated with solid CaO has been measured in the temperature range from 1823 to 2023 K. The equilibrium constant of reaction CaO (s)=Ca (mass pct in Ti,Ti-Al)+O (mass pct in Ti,Ti-Al) and the interaction parameter between calcium and oxygen were determined for Ti, TiAl, and TiAl₃. The standard Gibbs energy of reaction for TiAl was obtained as follows: $$\Delta G^\circ = 279,000 - 103TJ/mol$$ The possibilities for the deoxidation of titanium and titanium-aluminum alloys by using calcium-based fluxes are discussed.     

Effect of alloying elements on martensitic transformation in the binary NiAl(β) phase alloys

The characteristics of the B2(β) to L1₀(β′) martensitic transformation in NiAl base alloys containing a small amount of third elements have been investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD), and transmission electron microscopy (TEM). It is found that in addition to the normal Ll₀ (3R) martensite, the 7R martensite is also present in the ternary alloys containing Ti, Mo, Ag, Ta, or Zr. While the addition of third elements X (X: Ti, V, Cr, Mn, Fe, Zr, Nb, Mo, Ta, W, and Si) to the binary Ni₆₄Al₃₆ alloy stabilizes the parentβ phase, thereby lowering the M_s temperature, addition of third elements such as Co, Cu, or Ag destabilizes theβ phase, increasing the M_s temperature. The occurrence of the 7R martensite structure is attributed to solid solution hardening arising from the difference in atomic size between Ni and Al and the third elements added. The variation in M_s temperature with third element additions is primarily ascribed to the difference in lattice stabilities of the bcc and fcc phases of the alloying elements.     

Design and fabrication of W-Mo-Ti-TiAl-Al system functionally graded material

To obtain a kind of functionally graded material (FGM) with a density gradient, the W-Mo-Ti-TiAl-Al system graded material was designed, and the powder metallurgy method was chosen for its fabrication. The sintering of W, W-Mo, and Mo-Ti alloys at low temperature was studied, and then the approximately wholly dense W-Mo-Ti-TiAl system FGM was achieved by one-step sintering at 1473 K for 1 hour under a pressure of 30 MPa. It was found that through sintering at 1473 K, mainly the mechanical mixtures of W and Mo were formed in W-Mo alloys. In Mo-Ti alloys, the newly designed Fe-Al sintering aids not only have an important effect on the densification of the alloys, but also contribute to the formation of the (Mo, Ti) solid solution. However, the solid-solution reaction that occurred in Mo-Ti alloys was still insufficient. During the sintering of Ti + TiAl, the chemical reaction of Ti + TiAl → AlTi₂ was induced within the sintered body. The W-Mo-Ti-TiAl-Al system FGM was finally fabricated by joining of the TiAl side of the sintered W-Mo-Ti-TiAl system FGM to metal Al with an Al-based brazing filler metal, and its density changed quasi-continuously within the large range from 17.15 to 2.70 g/cm³.     

Phase transitions in reactive formation of Ti5Si3/TiAl in situ composites

A new method is developed for preparing Ti₅Si₃/TiAl in situ composites by incorporating metastable phases (called metastable precursors) into TiAl (a mixture of elemental Ti and Al) matrix powders. Metastable precursors with a starting composition of Ti-14Al-21Si are prepared by mechanical alloying (MA). They have been proven through X-ray diffraction (XRD) analysis and transmission electron microscope (TEM) observations to be mainly consisting of mixtures of nanostructured solid solutions and milling-formed TiAl compound. Particularly, phase reactions and transitions in the precursors and the composites during heating have been investigated in detail by using diffraction thermal analysis (DTA) in conjunction with XRD. It has been found that Ti₅Si₃ is in situ formed through a phase transition chain, TiSi₂ → Ti₅Si₄ → Ti₅Si₃. When the composite powder (precursor, Ti and Al) is heated, a combustion reaction first occurs in the matrix, which results in the formation of TiAl₃ and/or TiAl followed by the completion of the previously mentioned silicide transitions in a very short time. Scanning electron microscope (SEM) observations indicated the locations of reinforcements in the reaction-formed composite, and TEM observation provided some details of the structures for the reinforcements and their neighborhood. This method is intriguing because a designed phase hierarchy is possible.     

Chemical Vapor Synthesis of Titanium Aluminides by Reaction of Aluminum Subchloride and Titanium Tetrachloride

A new process for developing titanium aluminides (TiAls) using chemical vapor synthesis was investigated in a laboratory experiment. Aluminum subchloride (AlCl) was used as the reducing agent in the reaction with TiCl₄ and the source of aluminum for Ti-Al alloy. Two types of products, with large crystals and fine particles, were fabricated. The large crystals were determined to be TiAl, with small amounts of Ti and Ti₃Al phases. The composition of fine particles, on the other hand, varied in wide range.     

Microstructure and phase relations for Ti-Mo-Al alloys

The influence of aluminum additions to a Ti-7 at. pet Mo alloy on the phase equilibria was investigated. The microstructures of the alloys, Ti-7 pct Mo-7 pct Al and Ti-7 pct Mo-16 pct Al, were determined by light and electron microscopy. It was found that with increasing aluminum concentration the formation of the metastable w phase was suppressed. In the Ti-7 pct Mo-16 pct Al alloy the β phase decomposed upon quenching by precipitating coherent, ordered particles having a B2 type of crystal structure (β₂). At low temperatures the equilibrium phases for this alloy were β + α+ β ₂, whereas at high temperature (850° to 950°C) the Ti₃Al phase was in two-phase equilibrium with the β phase. The four-phase equilibrium which exists at a temperature of about 550°C involves the reaction β + Ti₃Al ⇌ α + β₂. G. LUETJERING, formerly Staff Member Materials Research Center, Allied Chemical Corp., Morristown, N. J.,     

Microstructure evolution in tial alloys with b additions: Conventional solidification

Solidification microstructures of arc-melted, near-equiatomic TiAl alloys containing boron additions are analyzed and compared with those of binary Ti-Al and Ti-B alloys processed in a similar fashion. With the exception of the boride phase, the matrix of the ternary alloy consists of the same α₂ (DO₁₉) and γ (Ll₀) intermetallic phases found in the binary Ti-50 at. pct Al alloy. On the other hand, the boride phase, which is TiB (B27) in the binary Ti-B alloys, changes to TiB₂ (C32) with the addition of Al. The solidification path of the ternary alloys starts with the formation of primary α (A3) for an alloy lean in boron (∼1 at. pct) and with primary TiB₂ for a higher boron concentration (∼5 at. pct). In both cases, the system follows the liquidus surface down to a monovariant line, where both α and TiB₂ are solidified concurrently. In the final stage, the α phase gives way to γ, presumably by a peritectic-type reaction similar to the one in the binary Ti-Al system. Upon cooling, the α dendrites order to α₂ and later decompose to a lath structure consisting of alternating layers of γ and α₂.     

Determination of dihedral angle distributions in polycrystals: Application to {itα} + {itβ} brass

A method is described to determine the distribution of dihedral angles of a given type in a polycrystalline aggregate from the measured distribution of angles in random sections. Each of the two angular distributions (2D and 3D) is divided inton classes and the probabilityp _ik that a dihedral angle in the 3D classk originates an angle in the 2D classi is calculated. Ann ×n matrixP = (_p) is then introduced to relate the two distributions. The 9 × 9 matricesP andP ^{- 1} corresponding to intervals of 20 deg are given in the paper. The method is applied to the determination of the distributions of dihedral angles atααβ andαββ triple lines in aα + β brass, submitted to a long annealing treatment at 620 °C. Using the average angles and the standard deviations of the distributions, the relative values of the interfacial tensionsact, ββ, and αβ were calculated. It was found that γ_αα ≃γ _ββ ≃ 14γ_αβ.     

机械球磨与反应烧结制备TiAl基合金

研究了机械球磨与反应烧结制备TiAl基合金的工艺,结果表明,Ti、Al单质混合粉末经机械球磨可得到具有Ti、Al相间层片结构的复合粉,且球磨时间越长,Ti/Al复合粉的层片结构越薄越均匀。将Ti/Al复合粉压坯在固相下进行扩散反应,Ti/Al之间的扩散反应随机械球磨时间的延长而加快,且球磨所得到的Ti/Al复合粉在固相下能够完全转变成Ti-Al金属间化合物。反应后得到的Ti-Al金属间化合物经过进一步的高温烧结,可以得到近全致密TiAl基合金,且得到了晶粒尺寸和层片厚度都比较小的典型的TiAl基合金组织。     

Pressure-assisted reactive synthesis of titanium aluminides from dense 50Al-50Ti elemental powder blends

In the present research, dense γ-TiAl based intermetallic samples were fabricated by reactive synthesis of fully dense elemental 50 at. pct Al-50 at. pct Ti powder blends. Two different processing routes were attempted: thermal explosion under pressure (combustion consolidation) and reactive hot pressing. In both approaches, relatively low processing or preheating temperatures (900 °C) were used. The entire procedure of thermal explosion under pressure could be performed in open air without noticeable oxidation damage to the final product. The application of a moderate external pressure (≤250 MPa) during synthesis was shown to be enough to accommodate the negative volume change associated with TiAl formation from the elemental components and, thereby, to ensure full density of the final product. Microstructure and phase composition of the materials obtained were characterized employing X-ray diffraction and scanning electron microscopy with energy dispersive analysis. It was found that at elevated temperatures(e.g., 900 °C), the equiatomic 50Al-50Ti alloy lies beyond the homogeneity range of the y-TiAl phase in the Ti-Al binary and contains, in addition to γ-TiAl, Al-rich Ti₃Al. Mechanical properties of the materials synthesized were evaluated in compression tests at different temperatures and by microhardness measurements. Due to its very fine microstructure, the Ti-Al material synthesizedvia reactive hot pressing exhibited superplastic behavior at temperatures as low as 800 °C. Formarly with the Department of Materials Engineering, Drexel University. This article is based on a presentation made in the “In Situ Reactions for Synthesis of Composites, Ceramics, and Intermetallics” symposium, held February 12–16, 1995, at the TMS Annual Meeting in Las Vegas, Nevada, under the auspices of SMD and ASM-MSD (the ASM/TMS Composites and TMS Powder Materials Committees).     

Microstructural analysis of multilayered titanium aluminide sheets fabricated by hot rolling and heat treatment

This study is concerned with the microstructural analysis of multilayered or bulk Ti aluminide sheets fabricated by the self-propagating high-temperature synthesis (SHS) reaction using hot rolling and heat treatment. Multilayered Ti/Al sheets were prepared by stacking thin Ti and Al sheets alternately, and a good Ti/Al interfacial bonding was achieved after rolling at 500 °C. When these sheets were held at 1000 °C, spheroidal TiAl₃ phases were formed by the SHS reaction at Ti/Al interfaces and inside Al layers. Microstructural analysis on the hot-rolled, multilayered Ti/TiAl₃ sheets revealed that intermetallic phases such as TiAl₂, TiAl, and Ti₃Al were formed at Ti/TiAl₃ interfaces due to interaction between Ti and TiAl₃ and that pores formed in the TiAl₃ layer were significantly reduced during hot rolling. When multilayered Ti/Ti aluminide sheets were heat treated at 1000 °C, Ti₃Al, TiAl, and TiAl₂ were grown as Ti and TiAl₃ were consumed. As the heat treatment proceeded, TiAl grew further, eventually leading to the fabrication of multilayered sheets composed of Ti₃Al and TiAl. Bulk Ti aluminide sheets, having a lamellar structure of Ti₃Al and TiAl, instead of multilayered sheets, were also fabricated successfully by heat treatment at 1400 °C. This fabrication method of the bulk sheets had several advantages over the method by hot forging or rolling of conventional cast Ti aluminides. From these findings, an idea to fabricate multilayered or bulk Ti aluminide sheets by hot rolling and heat treatment is suggested as an economical and continuous fabrication method, and the formation and growth mechanisms of interfacial phases are elucidated in this study.     

Synthesis of ductile titanium-titanium boride (Ti-TiB) composites with a beta-titanium matrix: The nature of TiB formation and composite properties

The study focused on the in-situ synthesis of titanium (Ti)-titanium boride (TiB) composites with β phase in the matrix by reaction sintering of TiB₂ with Ti and alloying element powders. The goal was to examine the nature of TiB whisker formation in three different kinds of powder mixtures: (1) β-Ti alloy powders and TiB₂; (2) α-Ti powder, a master alloy (Fe-Mo) powder containing the β-stabilizing elements, and TiB₂; and (3) α-Ti powder, a β-stabilizing elemental powder (Mo or Nb), and TiB₂. The effects of powder packing and the relative locations of powder particles on the morphological changes in TiB whisker formation and their growth were studied at processing temperatures ranging from 1100°C to 1300°C. The morphology, size, and distribution of whiskers were found to be influenced by the powder-packing conditions. A large particle-size ratio in bimodally packed mixtures led to the formation of a TiB monolithic layer around β grains. With a relatively finer starting powder, smaller size ratio, and trimodal packing arrangement, the TiB whiskers were found to be distributed more homogeneously in the matrix. The study also used the X-ray direct comparison method and the structure factor for the β phase to determine the volume fraction of TiB phase from X-ray data. Tensile tests and fractographic investigations were carried out on selected composites. The evolution of the composite microstructure, the influence of powder-packing variables, and the morphology and growth of TiB whiskers and their effect on mechanical properties are discussed.