Iron‐Rich Iron‐Titanium‐Silicon Alloys with Strengthening Intermetallic Laves Phase Precipitates

Two‐phase ternary Fe‐Ti‐Si alloys with Si contents from 2 to 16 at.% and Ti contents from 2 to 28 at.% were studied with respect to room temperature hardness, fracture strain and yield stress at room and higher temperatures up to 1150 °C. In addition oxidation was checked at temperatures between 400 and 1150 °C. The alloys are strengthened by precipitation of the stable Laves phase (Fe,Si)₂Ti which is a hard and brittle intermetallic phase. The yield stress as well as the brittle‐to‐ductile transition temperature (BDTT) increase with increasing Ti content. Yield stresses up to about 1400 MPa and BDTT between 100 °C and 600 °C with fracture strains of the order of 1 % below BDTT were achieved. The observed short‐term oxidation performance at temperatures up to 1150 °C compares favourably with that of Fe‐AI alloys with high Al contents.     

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.     

Development of Ti–Nb and Ti–Nb–Fe beta alloys from TiH2 powders

Ti–Nb β alloys are a promising alternative as an implant material due to their good properties and low Young’s modulus, compared to other Ti-alloys currently employed as biomaterials. In this study, three materials of the Ti–Nb and Ti–Nb–Fe systems were produced by powder metallurgy techniques starting from TiH₂ (TH) powder. Several sintering cycles were employed to evaluate the H₂ elimination and the effect of sintering temperature on densification and fraction of β-Ti phase. Also, the influence of alloying element size using two kinds of Fe powder was evaluated. The highest loss of H₂ was achieved by decreasing heating rate at the temperature range of hydride decomposition. SEM images and XRD results show mainly a β-Ti phase for TH–40Nb and TH–5Fe–25Nb samples. The TH–12Nb sample shows (α?+?β) microstructure. Fe addition with smaller particle size seems to improve the diffusion of Nb into Ti which promotes a higher β-phase fraction and sample homogeneity.     

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.     

Iron‐Rich Iron‐Aluminium‐Molybdenum Alloys with Strengthening Intermetallic μ phase and R phase Precipitates

Single‐phase and two‐phase ternary Fe‐Al‐Mo alloys with Al contents of usually 10 ‐16 at.% and Mo contents up to 42 at.% have been studied with respect to hardness at room temperature, yield stress and fracture strain at room temperature and higher temperatures up to 1000 °C and oxidation at temperatures of 400 ‐ 1000 °C. Thse alloys are strengthened by precipitation of the metastable R phase and/or the stable m phase depending on composition and heat treatment; both are hard and brittle intermetallic phases. The yield stress as well as the brittle‐to‐ductile transition temperature increases with increasing Mo content to reach yield stresses above 1400 MPa with, however, fracture strains below 1 % at temperatures below 800 °C. The observed short‐term oxidation is similar to that of other Fe‐Al alloys.     

Effects of ternary additions on the thermoelastic martensitic transformation of NiAl

Nickel-rich β-NiAl alloys, which are potential materials for high-temperature shape-memory alloys, show a thermoelastic martensitic transformation, which produces their shape memory effect. However, the transformation to Ni₅Al₃ phase during heating of NiAl martensite can interrupt the reversible martensitic transformation; consequently, the shape memory effect in NiAl martensite might not appear after heating. The phase transformation process in binary Ni-(34 to 37)Al martensite was investigated by differential thermal analysis (DTA) method, and we found that the condition of reversible martensitic transformation was not the β → Ni₅Al₃ transformation, but rather the M → Ni₅Al₃ transformation occurring at 250 °C to 300 °C. Therefore, the transformation temperature of M → Ni₅Al₃ determined the highest operating temperature for the shape memory effect. For verifying the critical temperature, the phase transformation process was investigated for eight ternary Ni-33Al-X alloys (X=Cu, Co, Fe, Mn, Cr, Ti, Si, and Nb). Only Ti, Si, and Nb additions were found to be effective in dropping the M _s temperature, and they facilitated the shape memory effect in Ni-33Al-X alloys. In particular, the addition of Si and Nb raised the transformation temperature of M → Ni₅Al₃, a potentially beneficial effect for shape memory at higher temperatures. This article is based on a presentation made in the symposium entitled “Fundamentals of Structural Intermetallics,” presented at the 2002 TMS Annual Meeting, February 21–27, 2002, in Seattle, Washington, under the auspices of the ASM and TMS Joint Committee on Mechanical Behavior of Materials.     

Microstructure evolution of Ti48AlχNb γ intermetallics

The microstructures of Ti48Al alloys containing either 2 at.% or 8 at.% Nb have been studied in as-cast, as-HIPped and in heat-treated samples. The as-cast Ti48Al2Nb and Ti48Al8Nb are heterogeneous and lower Nb content has been detected in the interdentritic γ by EDX analysis. Depending on the heat-treatment temperature and cooling rate, the microstructure obtained vary from martensitic structure in the water quenched samples to duplex structure consisting of γ grains and lamellar α₂/γ and to fully lamellar structure in the furnace cooled samples. Nb was found to have a high solubility in both α and γ phases and to expand the γ phase region so that a fully γ structure is obtained in the Ti48Al8Nb sample by annealing at 1200°C. A dense array of planar defects (antiphase boundaries, stacking faults and microtwins) was obtained in the Ti48Al8Nb alloy water quenched from 1400°C.     

Microstructure and Deformation Behaviour of Iron‐Rich Iron‐Aluminium Alloys with Ternary Carbon and Silicon Additions

The microstructure, hardness, yield stress, fracture strain, and brittle‐to‐ductile transition temperature of Fe‐Al alloys with Al contents of 12‐18 at.% Al, which are in the range of the so‐called K‐state with possible short‐range ordering reactions, and with ternary additions of carbon and silicon were studied with respect to the effects of possible impurities on the hardening of Fe‐Al alloys. It was found that perovskite‐type Fe₃AlC carbide particles precipitate even in alloys with low C and Si contents; they are controlled by prior heat treatments and strongly affect the deformation behaviour.     

Microstructural characterisation of Ti–Nb–(Fe–Cr) alloys obtained by powder metallurgy

Abstract

β alloys based on the Ti–Nb alloy system are of growing interest to the biomaterial community. The addition of small amounts of Fe and Cr further increases β-phase stability, improving the properties of Ti–Nb alloy. However, PM materials sintered from elemental powders are inhomogeneous due to restricted solid state diffusion and mechanical alloying provides a route to enhance mixing and elemental diffusion. The microstructural characteristics and bend strength of Ti–Nb–(Fe–Cr) alloys obtained from elemental powder mixture and mechanical alloyed powders are compared. Mechanical alloying gives more homogeneous compositions and particle morphology, characterised by rounded, significantly enlarged particles. In the sintered samples α and β phase are observed. The α phase appears at the grain boundaries and in lamellae growing inward from the edge, and is depleted in Nb. The β phase is enriched with Nb, Fe and Cr. The addition of Fe and Cr significantly increases the mechanical properties of Ti–Nb alloys, providing increased ductility.     

The effects of interstitials and hydrogen-interstitial interactions on low temperature hardening and embrittlement in V,Nb, and Ta

The effects of combined C and H on the temperature dependence of the yield stress and ductility of V, Nb, and Ta have been investigated at temperatures between 295 and 78 K. Because of the limited solubility of C in these metals, there was little solid solution hardening (S.S.H.). The combined effect of C and H on ductility was similar to that of H alone. There was no correlation between the ductile-brittle transition temperature (DBTT) and the temperature where hydrides formed (T _s. Comparison of the effects of C, N, and O on strengthening in both nonhydrogenated and hydrogenated V, Nb, and Ta showed that in general the contributions of C, N, or O and H were additive. C, N, and O produced athermal S.S.H. whereas the H contribution to the strengthening was thermally activated. The effect of these interstitials on ductility in nonhydrogenated V, Nb, and Ta was minimal, while their effect in hydrogenated V, Nb, and Ta was to decreaseT _s but have very little effect on the DBTT, which was determined primarily by the H content. There was no common correlation between the DBTT andT _s or between the temperature where pronounced strengthening occurred andT _s in the different alloys. Comparison of the results indicated that current models based on either hydride precipitates or H in solution as the cause of strengthening or embrittlement are incapable of explaining the observed effects of H on both the yield stress and the ductility in V, Nb, and Ta. T. E. SCOTT, formerly with Ames Laboratory     

Deformation Behaviour of Iron‐Rich Iron‐Aluminium Alloys with Ternary Transition Metal Additions

The hardness and yield stress at room temperature and the brittle‐to‐ductile transition temperature of Fe‐Al alloys with 16 at.% Al, which is in the range of the so‐called K‐state with possible short‐range ordering reactions, and ternary additions of 0.5 and 4 at.% of the transition metals Cr, Mo, Mn, V, Ti and Ni were studied with respect to possible hardening effects of the ternary additions. The addition of Cr, Mo and Mn to the Fe‐Al alloys produce solid‐solution hardening which corresponds to the hardening effect of Al. Only Ti, V and Ni produce extra hardening effects which cannot be related to solid‐solution hardening. This extra hardening is attributed to possible fine NiAl precipitates in the Fe‐Al‐Ni case and to possible enhanced short‐range ordering and/or fine carbide precipitates in the cases of Fe‐Al‐V and Fe‐Al‐Ti.     

Phase transformations in the (Ti,Nb)3 Al section of the TiAlNb system—II. Experimental tem study of microstructures

In Part I of this paper possible transformation paths that involve no long range diffusion and their corresponding microstructural details were predicted for TiAlNb alloys cooled from the high temperature b.c.c./B2 phase field into close-packed orthorhombic or hexagonal phase fields. In the present paper experimental TEM results show that two of the predicted transformation paths are indeed followed for different alloy compositions. For Ti25Al12.5Nb (at.%), the path includes the formation of intermediate hexagonal phases, A3 and D0₁₉, and subsequent formation of a metastable domain structure of the low-temperature O phase. For alloys close to Ti25Al25Nb (at. %), path involves an intermediate B19 structure and subsequent formation of a translational domain structure of the O phase. The path selection depends on whether B2 order forms in the high temperature cubic phase prior to transformation to the close-packed structure. The paper also analyzes the formation of a two-phase modulated microstructure during long term annealing 700°C. The thermodynamics underlying the path selection and the two-phase formation are also discussed.     

Phase Transformations in Third Generation Gamma Titanium Aluminides: Ti-45Al-(5, 10) Nb-0.2B-0.2C

Third generation γ-titanium aluminides with nominal compositions Ti–45Al–5Nb–0.2B–0.2C and Ti–45Al–10Nb–0.2B–0.2C were investigated to identify the phase transformation and their morphological stability with temperature. Electron microscopy and differential scanning calorimetry were employed for the characterization of phases and for recording the corresponding transformations, respectively. It has been inferred that the order–disorder transformation temperatures α₂ → α increased with increasing Niobium (Nb), while the α-transus temperature decreases. The stability of the microstructure for both alloys with temperature were also investigated. Mass change measured for the heating rates 20 °C s⁻¹ and 30 °C s⁻¹ reveals that the alloy Ti–45Al–10Nb–0.2–0.2C shows stability up to 1100 °C, and the alloy Ti–45Al–5Nb–0.2B–0.2C is stable up to 900 °C. The orientation relationship between the phases indicates that with the change in shape of the α phase from lamellar to equiaxed, it deviates from the Blackburn orientation relationship.

     

Metal injection moulding of low modulus Ti–Nb alloys for biomedical applications

Abstract

Titanium alloys containing β stabilising elements such as Nb, Zr and Ta are particularly promising as implant materials because of their excellent combination of low modulus, high strength, corrosion resistance and biocompatibility. A low elastic modulus is important for implants to avoid stress shielding and associated bone resorption. The difficulty of producing complex shapes of these alloys by conventional methods makes metal injection moulding (MIM) attractive. Ti–17Nb alloy parts with densities 94% of theoretical have been produced by MIM of a feedstock based on blended elemental powders. Scanning electron microscopy reveals a typical α?β Widmanstätten microstructure with a precipitated α phase layer along the grain boundaries. The parts exhibit an ultimate tensile strength of 768 MPa and a plastic elongation of over 5%. The modulus of elasticity, about 84 GPa, is more than 20% lower than that of cp Ti and Ti–6Al–4V.     

Isothermal oxidation behaviour of beta gamma powder metallurgy TiAl–4Nb–3Mn alloys

Abstract

A new TiAl–4Nb–3Mn beta gamma alloy was synthesised by a powder metallurgy process. HIPed and vacuum heat treated specimens were isothermally oxidised at 800 and 900°C in air up to 500 h. The TiAl–4Nb–3Mn alloys oxidised parabolically up to 500 h at both 800 and 900°C. The oxides consisted of outer TiO₂ layer, intermediate Al₂O₃ layer and inner TiO₂ rich mixed layer and the oxidation mechanisms of the alloy were identical at both temperatures. During oxidation, the degradation of α₂ lamellae in the vicinity of the interface forms a diffusion zone (lamellar depleted zone) leading to the formation of Nb and Mn rich white layers just below the interface by outward diffusion of Nb and Mn which are released from breakdown of α₂ lamellae. As exposure time increases, Nb begins to diffuse earlier than Mn and diffuses more actively at higher temperature. The activation energy for oxidation of TiAl–4Nb–3Mn alloy was lower than that of Ti–48Al alloy and was higher than those of Ti–48Al–2Nb–2Cr and Ti–48Al–2Nb–2Cr–W alloys.

On a synthétisé un nouvel alliage TiAl–4Nb–3Mn de type bêta gamma par un procédé de métallurgie des poudres. On a oxydé en isotherme à 800 et à 900°C à l’air, jusqu’à une durée de 500 heures, les spécimens pressés par HIP et traités thermiquement sous vide. Les alliages de TiAl-4Nb-3Mn s’oxydaient paraboliquement jusqu’à 500 heures tant à 800°C qu’à 900°C. Les oxydes consistaient en une couche externe de TiO₂, en une couche intermédiaire d’Al₂O₃ et en une couche interne mixe riche en TiO₂ et les mécanismes d’oxydations de l’alliage étaient identiques aux deux températures. Lors de l’oxydation, la dégradation de lamelles d’α₂ dans le voisinage de l’interface forme une zone de diffusion (zone lamellaire appauvrie) menant à la formation de couches blanches riches en Nb et en Mn juste au-dessous de l’interface par diffusion vers l’extérieur du Nb et du Mn, qui sont relâchés par la dégradation des lamelles d’α₂. À mesure que la durée de l’exposition augmente, le Nb commence à se diffuser plus tôt que le Mn et se diffuse plus activement à une température plus élevée. L’énergie d’activation pour l’oxydation de l’alliage de TiAl–4Nb–3Mn était plus basse que celle de l’alliage de Ti–48Al et était plus élevée que celle des alliages de Ti–48Al–2Nb–2Cr et de Ti–48Al–2Nb–2Cr–W.     

外科植入物用纯钛及其合金

主要介绍了外科植入物用新型钛合金的研究进展。到目前为止,研究出的外科植入物用钛合金从研究的时间顺序上可分为：（1）纯钛,Ti-6Al-4V合金;（2）Ti-6Al-7Nb合金（瑞士）,Ti-5Al-2.5Fe合金（德国）;Ti-2.5Al-2.5Mo-2.5Zr(TAMZ)合金（中国）;（3）新型β钛合金。概述了这些合金的研究现状、性能特点及其应用前景,并提出 了今后的发展方向。     

Phase equilibria in prototype Nb-Pd-Hf-Al alloys

The phase equilibria in two prototype alloys with nominal compositions 60Nb-20Pd-10Hf-10Al and 40Nb-30Pd-15Hf-15Al (in at. pct) are investigated using scanning electron microscopy and X-ray diffraction. The alloys were heat treated at 1200 °C and 1500 °C for 200 hours each. The phase analysis revealed that the alloys were, for the most part, in the three-phase equilibrium between (Nb), Pd₂HfAl, and Pd₃Hf. The compositions of these three phases along with other observed phases such as PdAl and (α-Hf) provide important data for establishing the Nb-Pd-Hf-Al quaternary phase diagram. A preliminary Nb-Pd-Hf-Al phase diagram, with pertinent tie-tetrahedra, was constructed based on the available composition data. The lattice parameters of (Nb), Pd₂HfAl, Pd₃Hf, and the coefficient of thermal expansion of Pd₂HfAl were measured, and models were developed to predict the composition dependence of the mean atomic volumes/lattice parameters of (Nb) and Pd₂HfAl and the temperature dependence of the lattice parameter of the (Nb) phase. The validity of the models was confirmed by good agreement between predicted and experimental values.     

WC含量对明弧堆焊奥氏体合金显微组织及耐磨性的影响

采用金属粉型药芯焊丝自保护明弧焊制备Cr9Mn6Nb2WVSi Ti奥氏体耐磨堆焊合金,借助XRD,SEM,EDS及光学显微镜研究外加WC颗粒对其显微组织及耐磨性的影响。结果表明,随焊丝药芯中WC增加,奥氏体晶粒细化,沿晶分布的多元合金化碳化物数量增加。初生γ-Fe相原位析出了(Nb,Ti,V)C相和残留WCx颗粒,起到晶内弥散强化作用,沿晶分布的(Nb,Ti,V)C和M_6C(M=Fe,Cr,Mn,V,W)相隔断了网状或树枝状的沿晶M_7C_3相,使其细化、断续分布而提高合金韧性,减轻沿晶碳化物数量增加的不利影响。硬度和磨损测试结果显示,明弧堆焊奥氏体合金洛氏硬度仅为40~47,但其磨损质量损失低于高铬铸铁合金,具有良好耐磨性;随外加WC含量提高,奥氏体合金晶内和晶界显微硬度差异显著减小,合金表面趋于均匀磨损而改善耐磨性。该奥氏体合金的磨损机制主要是磨粒显微切削,适用于带有一定冲击载荷磨粒磨损的工况下使用。     

Overview on Basic Types of Hot Rolling Textures of Steels

The present study gives a review on basic types of crystallographic textures developing during hot rolling of polycrystalline steels. The results are grouped into three fundamental classes of textures. The first group comprises pure Fe, some weakly bonded B2 and DO₃ structured intermetallics, as well as closely related alloys such as ferritic low carbon and microalloyed interstitial free steels. The second group includes highly alloyed corrosion‐resistant ferritic stainless and Fe‐Si transformer steels. Typical examples are steels with about 10 wt.%‐17 wt.% Cr, with about 3 wt.% Si, as well as body centered cubic transition metals such as Ta, Mo, and Nb which do not undergo any phase transformation during hot rolling. The third group comprises stable and instable austenitic stainless steels for instance on the basis of larger amounts of Cr and Ni or on Mn as well as duplex steels. Most L1₂ structured intermetallic alloys can also be assigned to this group. The suggested classification scheme is discussed in terms of different processing parameters, thermodynamics, microstructure, and crystallographic aspects.