Influence of thermodynamic activities of different masteralloys in pack powder mixtures to produce low activity aluminide coatings on TiAl alloys

Titanium aluminides are interesting high temperature materials, but show insufficient oxidation resistance as well as embrittlement at higher temperatures (>750 °C). Al-enriched coatings can be manufactured by pack cementation on many high temperature alloys to promote the formation of a protective alumina layer at high temperatures, which not only protects the alloy from oxidation but is also expected to impede embrittlement of TiAl at high temperatures. One drawback of such coatings is that Al-rich phases are very brittle. Therefore the major intermetallic aluminide phase in the coating plays a critical role for the protection behavior. Based on thermodynamic calculations different masteralloys were chosen to control the pack cementation process. Particular attention is given to the gradient between the aluminum activity of the different masteralloy powders and the aluminum activity of the substrate surface (alloy TNM^®-B1) in order to control the deposited phase at the surface. It is revealed that powder pack with Al as masteralloy provides a high Al activity and produces thick multi-layered coatings consisting of brittle TiAl₃ and TiAl₂ phase and aluminum-rich TiAl. By using different chromium aluminides as masteralloys, thinner, low-activity coatings could be produced, consisting of a bi-layer of brittle TiAl₂ phase and aluminum-rich TiAl or just the targeted pure aluminum-rich TiAl, which is known to have much better mechanical properties.     

Severe plastic deformation and hydrogenation of the titanium aluminides

Severe plastic deformation (mechanical activation in a hydrogen atmosphere and shear under pressure) effects on the hydrogenation of two titanium aluminides Ti₃Al and TiAl-type alloy (B2) have been studied. It is shown that a conventional hydrogenation of the bulk samples allows forming the hydrides with high hydrogen content and high desorption temperature: TiAl (773 K, 1.76 mass%) and Ti₃Al (1043 K, 2.94 mass%). In comparison with the conventional hydrogenation, the mechanical activation in a hydrogen atmosphere at room temperature allows one to obtain the hydrides of the TiAl (B2) and Ti₃Al alloys with the reduced desorption temperature: TiAl (453 K, 1.96 mass%) and Ti₃Al (531 K, 2.6 mass%). The shear under pressure has been applied to the sample before hydrogenation also leads to a reduction of the desorption temperature; however, it produces the phase transformation in the Ti₃Al intermetallic compounds, which lowers the observed a maximum hydrogen content.     

Si-modified aluminide coatings deposited on Ti46Al7Nb alloy by slurry method

Ti46Al7Nb alloy has been used as the research substrate material for the deposition of water-based slurries containing Al and Si powders. The diffusion treatment has been carried out at 950 °C for 4 h in Ar atmosphere. The structure of the silicon-modified aluminide coatings 40 μm thick is as follows: (a) an outer zone consisting of TiAl₃ phase and titanium silicides formed on the matrix grain boundaries composed of TiAl₃–type Ti₅Si₃; (b) a middle zone containing the same phase components with the matrix TiAl₃ and the silicides Ti₅Si₃, which formed columnar grains; (c) an inner zone, 2 μm thick, consisting of TiAl₂ phase. Cyclic oxidation tests were conducted in 30 cycles (690 h at high temperature) and showed a remarkably higher oxidation resistance of the Ti46Al7Nb alloy with the protective coating in comparison with the uncoated sample.     

Diffusion aluminide coatings for TiAl intermetallic turbine blades

Alloys based on intermetallic phases of a Ti–Al system are materials that, thanks to their resistance characteristics, can be widely used in automotive and aerospace applications. The main restriction for the use of Ti–Al materials is their insufficient oxidation resistance above 850 °C. Oxidation parameters might be improved by aluminide coatings based on TiAl₂ and TiAl₃ phases, which could induce the creation of an Al₂O₃ scale in the oxidation process. This type of aluminide could be deposited on the surface of TiAl alloys by various methods such as pack cementation, plasma spraying or magnetron sputtering. This article presents a new method of aluminide coating deposition on TiAl intermetallic alloys: out of pack technology. The investigated coating was deposited on turbine blades made of a Ti45Al5Nb intermetallic alloy. The surface morphology, structure, phase and chemical composition have been investigated using XRD phase analysis, SEM and EDS. The phase analysis showed that TiAl₃ and TiAl₂ were the main components of the deposited coating. An isothermal oxidation test of the TiAl turbine blades was conducted as well. After 1000 h of testing at 950 °C, the scale formed on the surface of the uncoated blades underwent spallation. The scale on the turbine blade with deposited aluminide coatings was very thin and no spallation was observed.     

Oxidation resistance and corrosion behavior of hot-dip aluminized coatings on commercial-purity titanium

Aluminizing is an effective method to protect alloys from oxidation and corrosion. In this article, the microstructure, morphology, phase composition of the aluminized layers and the oxide films were investigated by SEM, EDS and X-ray diffraction. The high temperature oxidation resistance and electrochemical behavior of hot dip aluminizing coatings on commercial-purity titanium had been studied by cyclic oxidation test and potentiodynamic polarization technique. The results show that the reaction between the titanium and the molten aluminum leads to form an aluminum coating which almost has the composition of the aluminum bath. After diffusion annealing at 950 °C for 6 h, the aluminum coating transformed into a composite layer, which was composed of an inner layer and an outer layer. The inner layer was identified as Ti₃Al or Ti₂Al phase, and the outer layer was TiAl₃ and Al₂O₃ phase. The cyclic oxidation treatment at 1000 °C for 51 h shows that the oxidation resistance of the diffused titanium is 13 times more than the bare titanium. And the formation of TiAl₃, θ-Al₂O₃ and compact α-Al₂O₃ at the outer layer was thought to account for the improvement of the oxidation resistance at high temperature. However, the corrosion resistance of the aluminized titanium and the diffused titanium were reduced in 3.5 wt.% NaCl solution. The corrosion resistance of the aluminized titanium was only one third of bare titanium. Moreover, the corrosion resistance of the diffused titanium was far less than bare titanium.     

Compton profile and charge transfer study in intermetallic Ti–Al system

The electronic structure of three intermetallic alloys namely Ti₃Al, TiAl and TiAl₃ in terms of Compton profiles is reported in this work. Directional Compton profiles are calculated for all the three alloys employing CRYSTAL code within the framework of density functional theory. The spherically averaged theoretical values are compared with the measurements made using 59.54 keV gamma-rays from Am²⁴¹ source. The calculations are in overall agreement with measurements in all cases. The measurements are also compared with the superposition of LCAO profiles of elemental solids. For Ti₃Al and TiAl₃ the LCAO values show better agreement whereas for TiAl the synthesized LCAO values are closer to the experiment. Effect of titanium 3d electrons is clearly visible in intermediate range of momentum in the Ti rich alloy. Charge transfer in the three alloys has also been estimated following the superposition of experimental profiles of Ti and Al metals. Comparison of Compton spectra of Ti₃Al, TiAl and TiAl₃ with the superposition of the Compton spectra of elemental constituents suggests a charge transfer of 2.8, 0.9 and 0.6 electron per Al atom, respectively. Such large values seem unreasonable and, therefore, this approach cannot be used for any reliable determination of the charge transfer in this system.     

Fabrication of TiAl intermetallic phases by heat treatment of warm sprayed metal precursors

Warm Spraying is an atmospheric coating process based on high-velocity impact bonding of powder particles. By decreasing the temperature of combustion gas via mixing with nitrogen the oxidation of feedstock powder can be effectively controlled. This is particularly important for Ti-based coating materials, which rapidly oxidize at elevated temperatures.In this study, Ti–Al composite coatings were fabricated by the Warm Spray process using a mixture of titanium and aluminum powders as a feedstock and applying a two-stage heat treatment at 600 and 1000 °C to obtain intermetallic phases. The microstructure, chemical and phase composition of the deposited and heat-treated coatings were investigated using SEM, EDS and XRD. The experimental results show that TiAl₃ was the first intermetallic phase formed during the first-stage heat treatment. The growth of TiAl₃ layer occurred mainly by diffusion of Al into Ti particles. Significant porosity that developed during the heat treatment was caused mainly by Kirkendall effect. After the second-stage heat treatment, a coating layer with TiAl as the dominant phase was obtained with about 20 vol % porosity.     

激光熔覆NiCr涂层的结构及摩擦学性能

利用激光熔覆技术在纯钛表面制备了NiCr涂层。用X射线衍射仪(XRD)和扫描电镜(SEM)分析了涂层的组成和组织结构。在UMT-2MT摩擦磨损试验机上对NiCr涂层在不同载荷和不同滑动速度下的摩擦磨损性能进行了测试。结果表明:NiCr涂层的主要组成物相为NiTi、Ni3Ti、Ni4Ti3、Cr2Ni3和Cr2Ti,涂层与基材冶金结合,涂层晶体结构主要为树枝状晶,涂层的平均显微硬度约为780HV0.2,涂层的摩擦因数随载荷和滑动速度的增加而减小;磨损率随载荷的增加而增加,随滑动速度的增加而减小。涂层的磨损率在10-6 mm3/Nm数量级,具有优异的耐磨性能。     

High temperature tribological characterisation of TiAlSiN coatings produced by cathodic arc evaporation

This study reports on the wear properties at medium-high temperatures of TiAlSiN films deposited by cathodic arc evaporation on hot work steel substrates. The chemical composition and microstructure of the coatings were characterised by glow discharge optical emission spectroscopy, scanning electron microscopy and X-ray diffraction. The mechanical properties, i.e. hardness and elastic modulus were evaluated by nanoindentation, and the adhesion of the coatings was tested by scratch tests. Coatings with stoichiometries of Ti_0.31Al_0.1Si_0.06N_0.53 and Ti_0.23Al_0.12Si_0.09N_0.55 exhibit microstructures consisting of solid solutions of (Ti,Al,Si)N, where Al and Si replace Ti atoms. These films show high hardness and good adhesion strength to the hot work steels. Conversely, coatings with a stoichiometry of Ti_0.09Al_0.34Si_0.02N_0.55 show a wurtzite-like microstructure, low hardness and poor adhesion strength.The wear rates of the coatings were investigated by ball-on-disc experiments at room temperature, 200 °C, 400 °C and 600 °C, using alumina balls as counter surfaces. At room temperature, the films show wear rates of the same order of magnitude of TiN and TiAlN coatings. On the other hand, the wear rates of solid solution (Ti,Al,Si)N coatings measured at 200, and 400 °C are one order of magnitude smaller than those measured at room temperature due to the formation of oxide-containing tribofilms on the wear tracks. At 600 °C the wear rates increase but still keep smaller than those measured at room temperature, although this effect can be influenced by the softening of the steel substrates by over-tempering. EDS analyses revealed that, between 200 °C and 400 °C, the oxidation of the coating occurs only at the contact zone between the film and the counterpart body due to the sliding process.     

冷轧热处理钛-铝箔制备微叠层Ti-Al系金属间化合物板材

通过钛箔、铝箔叠加烧结制备出微叠层Ti-Al系金属间化合物合金板材。对不同烧结条件下获得的板材组织和相组成进行分析。结果表明,当烧结温度到达到Al的熔点以上时,高温自蔓延反应（SHS）在Ti箔和Al箔之间发生,生成α-Ti、Ti3Al、TiAl、TiAl2和TiAl3等相;随着烧结时间的延长,α-Ti、TiAl2和TiAl3逐渐消失,最终获得包含Ti3Al和TiAl的叠层结构板材。由于铝的熔化,柯肯达尔效应和反应前、后摩尔体积的变化在烧结过程中产生大量的孔洞,随后的热压处理将孔洞消除并获得致密的合金板材。     

Solid-state hot pressing of elemental aluminum and titanium powders to form TiAl (γ + α2) intermetallic microstructure

The elemental powder metallurgy (EPM) process is used to prepare TiAl-base intermetallics. An EPM process conducted by two-stage solid-state hot pressing was employed to prepare TiAl-base intermetallics and to investigate the resulting microstructural changes. The results showed that the TiAl₃ phase forms in the first stage. During the temperature increase to the second sintering stage, lamellar phases start to precipitate in the TiAl₃ matrix. Further, the TiAl₃ phase transforms to TiAl, and Ti₃Al layers develop in the remaining titanium particles. Meanwhile, the lamellar phases grow into ring-type structures between the TiAl matrix and the Ti₃ Al layers. After the second stage, the remaining titanium particles are fully reacted, and a microstructure of Ti₃Al phases enclosed by fine-grained lamellar rings in the TiAl matrix is developed.     

Improvement of the oxidation and wear resistance of pure Ti by laser cladding at elevated temperature

NiCrBSi and NiCrBSi/WC-Ni composite coatings were produced on pure Ti substrates by the laser cladding technology. Thermal gravimetric (TG) analysis was used to evaluate the high temperature oxidation resistance of the laser cladding coatings. The friction and wear behavior was tested through sliding against the Si₃N₄ ball at elevated temperatures of 300 °C and 500 °C. Besides, the morphologies of the worn surfaces and wear debris were analyzed by scanning electron microscopy (SEM) and three dimensional non-contact surface mapping. The results show that the microhardness, high temperature oxidation resistance and high temperature wear resistance of the pure Ti substrates are greatly increased. For the pure Ti substrate, the wear behavior is dominated by adhesive wear, abrasive wear and severe plastic deformation, while both laser cladding coatings, involving only mild abrasive and fatigue wear, are able to prevent the substrates from severe adhesion and abrasive wear. In particular, the laser cladding NiCrBSi/WC-Ni composite coating shows better high temperature wear resistance than the NiCrBSi coating, which is due to the formation of a hard WC phase in the composite coating.     

Hard and superhard TiAlBN coatings deposited by twin electron-beam evaporation

Superhard nanostructured coatings, prepared by plasma-assisted chemical vapour deposition (PACVD) and physical vapour deposition (PAPVD) techniques, such as vacuum arc evaporation and magnetron sputtering, are receiving increasing attention due to their potential applications for wear protection. In this study nanocomposite (TiAl)B_xN_y (0.09 ≤ x ≤ 1.35; 1.07 ≤ y ≤ 2.30) coatings, consisting of nanocrystalline (Ti,Al)N and amorphous BN, were deposited onto Si (100), AISI 316 stainless steel and AISI M2 tool steel substrates by co-evaporation of Ti and hot isostatically pressed (HIPped) Ti-Al-B-N material from a thermionically enhanced twin crucible electron-beam (EB) evaporation source in an Ar plasma at 450 °C. The coating stoichiometry, relative phase composition, nanostructure and mechanical properties were determined using X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), in combination with nanoindentation measurements. Aluminium (∼ 10 at.% in coatings) was found to substitute for titanium in the cubic TiN based structure. (Ti,Al)B_0.14N_1.12 and (Ti,Al)B_0.45N_1.37 coatings with average (Ti,Al)N grain sizes of 5-6 nm and either ∼ 70, or ∼ 90, mol% (Ti,Al)N showed hardness and elastic modulus values of ∼ 40 and ∼ 340 GPa, respectively. (Ti,Al)B_0.14N_1.12 coatings retained their ‘as-deposited’ mechanical properties for more than 90 months at room temperature in air, comparing results gathered from eight different nanoindentation systems. During vacuum annealing, all coatings examined exhibited structural stability to temperatures in excess of 900 °C, and revealed a moderate, but significant, increase in hardness. For (Ti,Al)B_0.14N_1.12 coatings the hardness increased from ∼ 40 to ∼ 45 GPa.     

Microstructure, mechanical and wear properties of laser processed SiC particle reinforced coatings on titanium

Laser processing of Ti-SiC composite coating on titanium was carried out to improve wear resistance using Laser Engineered Net Shaping (LENS™) — a commercial rapid prototyping technology. During the coating process a Nd:YAG laser was used to create small liquid metal pool on the surface of Ti substrate in to which SiC powder was injected to create Ti-SiC metal matrix composite layer. The composite layers were characterized using X-ray diffraction, scanning and transmission electron microscopy equipped with fine probe chemical analysis. Laser parameters were found to have strong influence on the dissolution of SiC, leading to the formation of TiSi₂, Ti₅Si₃ and TiC with a large amount of SiC on the surface. Detailed matrix microstructural analysis showed the formation of non-stoichiometric compounds and TiSi₂ in the matrix due to non-equilibrium rapid solidification during laser processing. The average Young's modulus of the composite coatings was found to be in the range of 602 and 757 GPa. Under dry sliding conditions, a considerable increase in wear resistance was observed, i.e., 5.91 × 10^− 4 mm³/Nm for the SiC reinforced coatings and 1.3 × 10⁻³ mm³/Nm for the Ti substrate at identical test conditions.     

State of Intermetallics Development

A brief overview is given on the state of development of intermetallic alloys for high-temperature applications with discussion of problems and prospects. In particular alloys on the basis of the titanium aluminides Ti₃Al and TiAl, the nickel aluminides Ni₃Al and NiAl, the iron aluminides Fe₃Al and FeAl, chromides and silicides are regarded.     

Sulfidation properties of TiAl–2 at.% X (X=V,Fe, Co,Cu, Nb,Mo, Ag and W) alloys at 1173 K and 1.3 Pa sulfur pressure in an H2S–H2 gas mixture

TiAl–2 at. % X (X=V, Fe, Co, Cu, Nb, Mo, Ag and W) alloys were sulfidized at 1173 K for 86.4 ks at a 1.3 Pa sulfur pressure in an H₂–H₂S gas mixture. The structure, phases, and compositions of the external sulfide scale and alloy surface layer were measured using EPMA and X-RD. The TiAl–2Ag and –2Cu alloys sulfidized faster than TiAl, and the alloy surface layer was thicker than that of TiAl. Sulfidation amounts of the TiAl–2X (X=V, Co, Fe, Mo, W and Nb) alloys were almost the same as that of TiAl, while the thickness of the alloy surface layer decreased in the order: V>Co>Fe>Mo>[Cr (by Narita T, Izumu T, Yatagai M, Yoshioka T. Intermetallics, 2000;8:371)]>W>Nb. The sulfide scale was composed of multi-layer structures: an outermost (rich in Ti-sulfides), an outer (rich in Al₂S₃), an inner (a mixture of Ti-sulfides and Al₂S₃), and an innermost (rich in Ti-sulfides) layer. The alloy surface layer also had a multi-layer structure, and was classified into four groups: group 1 for TiAl–2V and –2Co alloys as well as TiAl binary alloy where the surface layer consists of alloy substrate/TiAl₂/TiAl₃/sulfide scale, group 2 for TiAl–2Nb, –2Mo, and –2W (and also– 2Cr) alloys with alloy substrate/TiAl₂/TiAl₃/(Nb, Mo, W or Cr)–Al alloy/sulfide scale, group 3 for TiAl–2Cu and –2Ag alloys with alloy substrate/TiAl₂/Ti (Al, Ag or Cu)₃ with an L1₂ structure/TiAl₃/sulfide scale, and group 4 for TiAl–2Fe alloy with alloy substrate/TiAl₂/Ti(Al,Fe)₃ with an L1₂ structure/TiAl₃/FeAl₃/sulfide scale. Diffusion paths for these four groups were shown in a tentative Ti–Al–X ternary phase diagram.     

A comparative study on Ti1 − xAlxN coatings reactively sputtered from compound and from mosaic targets

The aim of this work is to illuminate the influence of two widely applied target types, i.e. TiAl compound targets produced by powder metallurgy and mosaic TiAl targets, on the sputter deposition process as well as on the structure and properties of the obtained coatings. After development of a sputter process for the compound targets by optimization of cathode power and nitrogen partial pressure, this process was compared to the commercially applied mosaic target process by taking into account the sputter yields of Ti and Al and the respective deposition rates. The deposition rate achieved with the compound targets was ~ 44% higher than that obtained for the mosaic targets. The Al content in the coatings deposited from the compound targets was slightly higher and the domain size of the formed cubic Ti_1 − xAl_xN solid solution considerably larger than for the coatings deposited from the mosaic targets. The coatings grown from the compound targets showed, in contrast to those synthesized from the mosaic targets, tensile stresses. While the hardness of the coatings sputtered from the compound targets was slightly below that of the coatings synthesized from the mosaic targets, both their friction and wear behavior were slightly improved. In summary, it could be shown that using compound TiAl targets manufactured by powder metallurgy, Ti_1 − xAl_xN coatings with mechanical and tribological properties comparable to those grown from commercially applied mosaic targets can be deposited at significantly higher growth rates.     

Microstructure characteristics of Ti3Al/TiC ceramic layer deposited by laser cladding

Al + TiC laser cladding coatings were prepared on Ti-6Al-4V alloy by CO₂ laser cladding technique. The microstructure, micro-hardness and phase constitutes of the laser cladding layer were investigated by means of scanning electron microscope (SEM), X-ray diffraction (XRD) and microsclermeter. The results indicated that the laser cladding layer solidified into the fine microstructure rapidly, and TiC hard phase was dispersived in the cladding layer. When the mass percent of TiC was 40%, the micro-hardness (1100HV_0.2-1250HV_0.2) of Al + TiC cladding layer was 3 times more than that of the Ti-6Al-4V alloy substrate (350-370HV_0.2). The cladding layer mainly consisted of α-Ti (Al), β-Al (Ti), Ti₃Al, TiAl, Al₃Ti and TiC phase. There phases were beneficial to improve the hardness and wear resistance of the cladding layer.     

Characterization of nanocrystalline AlTiN coatings synthesized by a cathodic-arc deposition process

Graded and multilayered Al_xTi_1−xN nanocrystalline coatings were synthesized by using cathodic-arc evaporation (CAE) process. Ti₃₃Al₆₇ and Ti₅₀Al₅₀ alloy cathodes were used for the deposition of Al_xTi_1−xN nanocrystalline coatings with different Al/(Ti+Al) ratios. Optical emission spectra of the plasma species including atomic and ionized Ti, atomic Al, excited and ionized nitrogen (N₂ and N₂⁺) revealed that the excitation, ionization and charge transfer reactions of the Al-Ti-N plasma occurred during the Al_xTi_1−xN coating process. A preferred (111) orientation was shown in the Al_0.67Ti_0.33N with high Al/(Ti+Al) atomic content ratio (0.63) and small grain size (29 nm). The graded Al_0.67Ti_0.33N/TiN possessed the highest hardness of Hv_25 g 3850 ± 180. However, the multilayered Al_0.67Ti_0.33N/TiN coating supported a longer tool life with lower residual stress. It has been found that the wear performance and mechanical properties of the films were correlated with the Al/(Ti+Al) content ratio and multilayered structure.     

Preparation of TiAl3-Al composite coating by cold spraying

TiAl₃-Al coating was deposited on orthorhombic Ti₂AlNb alloy substrate by cold spraying with the mixture of pure Al and Ti as the feedstock powder at a fixed molar ratio of 3:1 when the spraying distance, gas temperature and gas pressure for the process were 10 mm, 250 °C and 1.8 MPa, respectively. The as-sprayed coating was then subjected to heat treatment at 630 °C in argon atmosphere for 5 h at a heating rate of 3 °C/min and an argon gas flow rate of 40 mL/min. The obtained TiAl₃-Al composite coating is about 212 μm with a density of 3.16 g/cm³ and a porosity of 14.69% in general. The microhardness and bonding strength for the composite coating are HV525 and 27.12 MPa.