Improving the oxidation resistance of γ‐titanium aluminides by halogen treatment

Intermetallic alloys based on TiAl are candidates for several structural high temperature applications but their oxidation resistance is limited to temperatures below 800 °C. In this paper the results of high temperature oxidation and creep tests will be presented and discussed. The treatment with halogens improves the oxidation resistance of these alloys up to 1050 °C. A thin protective Al₂O₃‐layer is formed after treatment with halogens instead of the mixed TiO₂/Al₂O₃/TiN scale typically grown on these alloys. This alumina layer protects the component under isothermal and thermocyclic conditions. The protective effect is stable up to at least 8760 h. Creep tests of halogen treated materials at high temperatures showed no effect on the creep behaviour. Automotive turbocharger rotors were exposed at 1050 °C in air with and without fluorine‐treatment for demonstration of real parts.     

Kinetic study on NaF-activated pack-aluminizing of pure titanium at 950–1100 °C

Pure titanium samples were aluminized at 950, 1025 and 1100 °C for 0-6 h in a pack containing 10%Al+5%NaF+ 85%Al₂O₃ in mass fraction. The aluminized layers formed on the samples were characterized. The kinetic studies indicated that the diffusion of Al-bearing gases through the pack is the rate-controlling step in this process. The activation energy of 161.8 kJ/mol was calculated for this step. In addition, the mass gains of the aluminized samples were predicted using the partial pressures of gases in the pack and those adjacent to the samples surface. The predicted values are in good agreement with the experimental measurements at 950 °C but are higher than those measured at 1025 and 1100 °C.     

Simultaneous chromizing — Aluminizing coating of low-alloy steels by a halide-activated,pack-cementation process

The simultaneous chromizing — aluminizing of low-alloy steels has achieved Kanthal-like surface compositions of 16–21Cr and 5–8 wt.% Al by the use of cementation packs with a Cr-Al masteralloy and an NH₄Cl activator salt. An initial preferential deposition of Al into the alloy induces the phase transformation from austenite to ferrite at the 1150°C process temperature. The low solubility of carbon in ferrite results in the rejection of solute C into the austenitic core, thereby preventing the formation of an external Cr-carbide layer, which would otherwise block aluminizing and chromizing. The deposition and rapid diffusion of Cr and Al into the external bcc ferrite layer follows. Parabolic, cyclic-oxidation kinetics for alumina growth on the coated steels in air were observed over a wide range of relatively low temperatures (637–923°C).     

High-temperature oxidation of titanium silicide coatings on titanium

Coatings of Ti ₅Si₃ on titanium have been prepared by means of decomposition of silane SiH₄ on heated titanium ribbons. Oxidation of the coated titanium specimens was much slower than that of the noncoated ones. Gravimetric and morphological experiments allowed to propose a mechanism describing the oxidation process.     

高铌钛铝合金高温固态置氢组织与高温变形行为

研究了高铌钛铝合金Ti-44Al-8Nb高温固态置氢处理组织演化规律,并考察了氢对高温变形行为的影响。研究结果表明,具有近片层组织结构的Ti-44Al-8Nb合金吸氢过程是吸热过程,合金的吸氢量随着置氢温度、置氢时间、氢流量的提高逐渐提高;在1200℃下进行固态置氢和等温热处理,置氢后的合金片层粗化,B2相含量较高;在T_α温度以上置氢后,氢降低界面能促使片层团界面光滑平整;氢对高铌钛铝合金的高温变形行为有明显的影响,在1200℃,应变速率为0.01s_-1下变形,添加0.043wt%H后,峰值应力降低40%。高温固态置氢能够有效改善高铌钛铝合金热加工性能。     

Alloy design of gamma titanium aluminides based on phase diagrams

Phase stability in the Ti---Al---X (X = Cr, Mo and W) system has been investigated at 1473 and 1573 K by the following methods: microstructure observation of quenched specimens, diffusion coupling experiments, thermal analysis of DTA and in situ observation of X-ray diffraction. The ternary phase diagrams of Ti---Al---X system are proposed; additions of Cr, Mo and W stabilize the β phase in the ternary phase diagrams. The tendency of ‘β stabilizer’ is in the following order: 6 at% Cr = 3 at% Mo = 1 at% W 10 vol% β phase. In these Ti-Al-X ternary systems, the + β + γ three-phase coexisting region is close to the Ti---Al binary line and sifts slightly toward a higher concentration of Al as temperature increases. Based on the ternary phase diagrams, (γ + β) TiAl having a super-plastic capability and partial lamellar (P-L) microstructure which shows relatively well balanced mechanical properties from room temperature to elevated temperatures have been rationalized.     

Development and growth of boron-modified and germanium-doped titanium-silicide diffusion coatings by the halide-activated,pack-cementation method

A halide-activated, cementation pack has been developed to codeposit either silicon and boron or else silicon and germanium in a single processing/reaction step to grow Ti-silicide diffusion coatings on commercially pure (CP) titanium, Ti-22Al-27Nb, and Ti-20Al-22Nb. Since boron is nearly insoluble in TiSi₂, a TiB₂ layer is localized at the surface of the B-modified silicide coatings. The thickness of the TiB₂ layer is controlled by the choice of boron activity and halide activator in the pack. Germanium is soluble in the Ti-silicide layers but inhomogeneously distributed in the Ge-doped silicide coating. The germanium content is controlled by choices of the Si-to-Ge ratio and the halide activator in the pack. The growth kinetics for the five-layered B-modified silicide coatings are generally similar to the undoped silicide coatings. The growth mechanism for the five-layered Ge-doped silicide coatings is generally different from the undoped silicides. The growth of dual-layer Ti-boride coatings was also studied.     

Laser cladding of titanium alloy coating on titanium aluminide alloy substrate

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High-temperature oxidation of titanium diboride of different purity

Oxidation in air of TiB₂ powders of two different types in the temperature range from 100 to 900°C as well as of compact samples produced from them (at 600–1200°C) was studied by DTA, thermogravimetry, X-ray analysis, AES, EPMA, and SEM methods. The admixture elements in powders were found to prevent oxygen from enriching the diboride surface. In compact TiB₂ samples impurities form diffusion barriers during oxidation at the matrix/scale and scale/gas interfaces as well as facilitate sintering of the scale being formed.     

Cast structure and property variability in gamma titanium aluminides

Aspects of cast structure that influence mechanical property variability, and in particular tensile ductility, have been studied in a Ti-48Al-2Cr-2Nb titanium aluminide alloy. Macrostructure, porosity, microstructure and tensile properties have been characterized over a range of casting processing conditions. Local solidification times and subsequent solid-state cooling rates during casting have been characterized via local thermal measurements in combination with solidification modeling. Large variations in cooling rate during casting dramatically influence the initial cast structure as well as the distribution of defects such as porosity. Variations in as-cast structure persist through subsequent thermal and hot isostatic pressing cycles and contribute to the variability of tensile ductility. The current understanding of the relationship of tensile ductility to processing-induced changes in structure will be briefly discussed.     

Twinning and mechanical behavior of titanium aluminides and other intermetallics

Based on the recent studies of deformation twinning in ordered intermetallics, the general background on slip-twinning-microcracking relationships is established. Specific roles of deformation twinning in the generalized plasticity of polycrystals and the crack-tip microplasticity are discussed in terms of the local strain compatibility by invoking both ‘tension’ and ‘compression’ twins. Special examples are given for γ-TiAl, other L1₀ alloys, and Ti₃Al of the D0₁₉ structure. Effects of composition, microstructure and temperature on defect properties that are relevant to the propensity of deformation twinning are discussed.     

High-temperature oxidation of titanium carbide in oxygen

The kinetics of titanium carbide oxidation in oxygen over the temperature range of 600–1200°C and oxygen pressure from 0.1 to 740 Torr have been studied with a vacuum microbalance. Layer-by-layer x-ray analysis, petrography, metallography, and gas chromatography have been used to analyze the oxidation products. A paralinear nature of the oxidation of material was established, and the rate constants of the process were calculated for the corresponding parabolic and linear portions of the kinetic curves. It was shown that a gaseous product, CO₂, formed, as well as a solid product, TiO₂ (rutile), both stoichiometric and nonstoichiometric. The lower oxides, Ti₃O₅, Ti₂O₃, TiO, were noted in the scale at temperatures from 700 to 800° and low oxygen pressures, their relative quantity rising with decreasing pressure. Based on x-ray analysis and microhardness measurements, it was concluded that titanium oxicarbides formed in the TiC, directly adjacent to the scale. A possible oxidation mechanism of titanium carbide is proposed.     

High-temperature oxidation of Fe3Al-based iron aluminides in oxygen

The isothermal high-temperature oxidation behavior of Fe₃Al-based iron aluminides in oxygen has been studied. Fe–25Al was oxidized at 1225, 1330, 1425 and 1530 K, while Fe–28Al, Fe–24Al–5Cr, Fe–24Al–5Ti, Fe–28Al–2Cr and Fe–30Al–4Cr (all compositions in atom percent) were oxidized at 1330 K. The weight gain data were analyzed and rate constants (k_p) determined by assuming a parabolic rate law. The variations of instantaneous parabolic rate constant with time reflected the complexity of the oxidation behavior. These have been attributed to the changes taking place in the nature and properties of the scale as a function of time. The values of k_p for oxidation of Fe₃Al were one to two orders of magnitude lower than those for Ti₃Al-based intermetallics. As revealed by X-ray diffraction, the scale formed on Fe–25Al was predominantly α-Al₂O₃ at higher temperatures, while θ-Al₂O₃ was observed after oxidation at lower temperatures. The observed kinetics matched with α-Al₂O₃-formation kinetics at higher temperatures and θ-Al₂O₃-formation kinetics at lower temperatures. For all the other intermetallics, only α-Al₂O₃ was identified at 1330 K. The whisker morphology of θ-Al₂O₃ and the ridged morphology of α-Al₂O₃ were confirmed by scanning electron microscopy. Alloying with Cr or Ti increased the oxidation rate of iron aluminides, especially during the initial stages. Addition of Ti changed the nature, color, and morphology of the scale, leading to improved adherence.     

Analyses of the gaseous species in halide-activated cementation coating packs

The partial pressures of equilibrium gaseous species in pack-cementation diffusion processes using pure condensed Al(l), Cr(s), and Si(s) metals activated by various halide salts under Ar or reducing environments which contain different amounts of hydrogen have been calculated. The analyses indicate that the presence of hydrogen gas in the system does not significantly alter the equilibrium partial pressures of gaseous species for a pack containing Al at unit activity. In general, the partial pressures of CrCl₂ and SiCl₂ are higher in a chloride-activated pack than in a fluoride-activated pack. Therefore, the codeposition of Cr or Si with Al is possible when a chloride salt is used as the activator with a masteralloy of composition dilute in Al. The addition of hydrogen to the gas phase decreases the partial pressure of Cl₂ and thereby the partial pressures of CrCl₂ and SiCl₂. However, the presence of hydrogen and the formation of hydrogen halides and metal hydrides could increase the kinetics of the transporting processes, particularly for the coatings of Cr and Si. The study also indicates that the vapor pressures for the volatile chlorides of Fe are significantly higher than those for Ni or Co, so that displacement reactions leading to the loss of Fe from the substrate are expected for coating processes involving high halide activities.     

Investigation on the oxidation behaviour of gamma titanium aluminides coated with thermal barrier coatings

In the present study, the applicability of thermal barrier coatings (TBCs) on γ‐TiAl alloys was investigated. Two alloys with the chemical compositions of Ti‐45Al‐8Nb‐0.2B‐0.15C and Ti‐45Al‐1Cr‐6Nb‐0.4W‐0.2B‐0.5C‐0.2Si were used. Before TBC deposition, the specimens were pre‐oxidised in laboratory air or low partial pressure oxygen atmosphere. Yttria partially stabilised zirconia top coats were then deposited using electron‐beam physical vapour deposition (EB‐PVD). The oxidation behaviour of the γ‐TiAl specimens with TBC was studied by cyclic oxidation testing in air at 850 and 900 °C. Post‐oxidation analysis of the coating systems was performed using scanning electron microscopy with energy‐dispersive X‐ray spectroscopy (EDS). No spallation of the TBC was observed for pre‐oxidised specimens of both alloys when exposed to air at 850 °C for 1100 cycles of 1 h dwell time at high temperature. SEM micrographs of the thermally grown oxide scale revealed outer mixed TiO₂/Al₂O₃ protrusions with a columnar structure. The protrusions contained small particles of zirconia and a low amount of about 0.5 at% zirconium was measured by EDS analysis throughout this outer oxide mixture. The TBCs exhibited excellent adherence on the oxide scale. Intercolumnar gaps and pores in the root area of the TBC were filled with titania and alumina. Below the outer columnar oxide scale, a broad porous zone of predominant titania was observed. The transition region between the oxide scale and substrate consisted of a discontinuous nitride layer intermixed with alumina particles and intermetallic phases rich in niobium formed at the nitride layer/substrate interface. When thermally cycled at 900 °C, the oxide scales on the alloy Ti‐45Al‐8Nb‐0.2B‐0.15C pre‐oxidised in low partial pressure oxygen spalled off after 540 cycles. For the sample with TBC, spallation was observed after 810 cycles. Failure occurred in the thermally grown oxide near the oxide/nitride layer interface. Microstructural examinations revealed again oxide scales with columnar structure beneath the zirconia top coat and good adherence of the TBC on the thermally grown oxides formed at 900 °C.     

Oxidation mechanism of titanium nitride in oxygen

Despite the apparent complexity of the linear oxidation of titanium or titanium nitride resulting from the formation of a layered structure of the rutile scale formed, the uniqueness of the mechanism is proven. The limiting step appeared to be the predominant short-circuit diffusion of oxygen (E 44 kcal · mole^–1) through a rutile lamella of variable thickness growing at the nitride-oxide boundary and fracturing periodically to form a detached porous layer through which molecular oxygen can penetrate. The pressure dependence of the diffusion process in the case of the nitride was associated with the outward migration of nitrogen, while the undulations of the kinetics under certain conditions were caused by the growth of a sintered, recrystallized outer zone of oxide. The periodic exfoliation of the oxide was related to its poor adherence to the substrate, certainly due to the presence at the nitride-oxide interface of a thin gray film probably composed of intermediate phases between TiN_x (or Ti) and TiO₂.     

High-temperature precision forming of titanium blades

Based on the experimental study of superplastic deformation parameters, a technology was developed for producing near-net-shape compressor blade forgings for gas turbine units from Ti-6.2Al-2.5Mo-l.5Cr-0.2Si-0.5Fe. The mechanical properties of these blades are higher than those of blades produced by conventional methods, and the anisotropy coefficient is reduced. The improved properties of the blades can be attributed to the isotropy of mechanical properties resulting from the homogeneous fine-grained equiaxed structure produced throughout the blade volume.     

钛及钛合金表面转化膜的应用及发展

对钛及钛合金的表面转化膜处理技术进行了综述,主要包括化学氧化、阳极氧化、硅烷化、磷酸盐转化等。阐述了各种处理方法的工艺过程及其作用效果,分别指出了各种方法的优缺点。同时展望了其今后的应用及发展前景。     

The halogen effect in the oxidation of intermetallic titanium aluminides

Stoichiometric TiAl and two quasi-technical TiAl alloys were investigated in the temperature range of 800-1000°C with regard to the halogen microalloying effect on oxidation resistance. The halogens Br, Cl, F and I were introduced into the material surface by ion implantation with different doses and energies before the thermogravimetric oxidation experiments were started. The results show that a very low “homeopathic” amount of these halogens at the oxide scale/metal interface activates a mechanism of selective Al-oxidation which changes oxidation behavior from fast mixed titania/alumina kinetics to slow pure alumina kinetics. A model is described which explains this change in kinetics supported by quantitative data from thermodynamic calculations. The halogen microalloying effect offers a high potential for the improvement of oxidation resistance of TiAl alloys for technical applications.     

合金元素对典型阻燃钛合金燃烧行为的影响

阻燃钛合金是飞机发动机核心部件中的重要材料，由于钛合金燃烧过程难以控制，燃烧参数难以获得加大了研究难度。论文以典型阻燃钛合金Ti40和Ti14为研究对象，利用高速摄影在不同氧分压环境下通过直流点火研究其燃烧行为，探索其燃烧过程中的氧扩散过程，明确合金元素对阻燃行为的影响 。研究发现两种合金燃烧后均形成分层结构，Ti40合金中Cr和V元素向外扩散，和氧反应生成Cr2O3/V2O5，密度高于TiO2的密度，Ti原子很难通过Cr2O3向外扩散与氧反应，提高燃烧表面致密度，抑制氧的扩散；而对于Ti14合金，共析反应生成大量的液相，富Cu相包裹Ti相球化晶粒形成Cu元素富集层，隔离氧并减少钛与氧的接触，从而降低氧向基体的扩散速率，同时Cu相的包裹作用增加氧扩散的距离，氧需要更多的能量扩散与Ti接触并反应，从而抑制了反应的发生。