High temperature corrosion mechanisms of certain new TiAl-based intermetallic alloys in an aggressive H2/H2O/H2S environment at 850 °C

High temperature corrosion behaviour of three TiAl-based intermetallic alloys - Ti-44Al-8Nb-1B, Ti-46Al-8Nb-1B and Ti-48Al-2Nb-2Cr-1B (at.%) - was studied in an environment of H₂/H₂S/H₂O yielding p_S2 ∼ 6.8 × 10⁻¹ Pa and p_O2 ∼ 1.2 × 10⁻¹⁵ Pa potentials at 850 °C. The kinetic results obtained by a discontinuous gravimetric method indicate that increase in Al and Nb concentrations led to enhanced high temperature corrosion resistance, the corrosion resistance decreasing in the order: Ti-46Al-8Nb-1B > Ti-44Al-8Nb-1B > Ti-48Al-2Nb-2Cr-1B. The scale development studies using SEM, TEM, EDX, WDS and XRD confirmed the formation of a multilayered scale on all materials. An outer layer consisting of TiO₂ existed beneath which an Al₂O₃ layer was present. Then a layer of TiO₂ formed again, below which an Al-enriched NbAl₃ was observed. A TiS layer was found beneath the NbAl₃ layer. The formation of TiS led to the development of a NbAl₃ band between the multilayered scale and the substrate.     

Preparation and oxidation resistance of a crack-free Al diffusion coating on Ti22Al26Nb

A crack-free Al diffusion coating has been developed to improve the oxidation resistance of Ti22Al26Nb. It was produced by a two-step method; an Al film was deposited on the substrate alloy by arc ion plating followed by a diffusion process conducted at 873 K in pure Ar to form the Al diffusion coating. The two-step method lowers the temperature required to form the diffusion coating, which dramatically decreases the thermal stress developed in the coating and results in it being crack-free. The oxidation resistance of the non-coated Ti22Al26Nb alloy in isothermal and cyclic tests in air at 1073 K was poor, but the coated specimens possessed excellent oxidation resistance because a protective α-Al₂O₃ scale formed. The life of the Al diffusion coating greatly depends upon the rapid initial formation of a protective Al₂O₃ scale and interdiffusion between coating and substrate. Once the stable Al₂O₃ scale has formed and the composition changes from (Ti, Nb)Al₃ into (Ti, Nb)Al₂, the coating has a long life.     

Oxidation behavior of Ti–46Al–8Nb alloy with boron and carbon addition under thermal cycling conditions

Oxidation behavior of Ti–46Al–8Nb (in at.%) alloy with boron and carbon addition under thermal cycling conditions was investigated. Oxidation of Ti–46Al–8Nb, Ti–46Al–8Nb–1B and Ti–46Al–8Nb–1B-0.25C (in at.%) alloys was carried out at 1073 K in laboratory air for 42 cycles (1 cycle, 24 h), 1008 h in total. The mass loss rates of Ti–46Al–8Nb and Ti–46Al–8Nb–1B measured during the oxidation were similar. The best oxidation resistance was found for Ti–46Al–8Nb–1B-0.25C alloy with the smallest mass change. XRD and SEM-EDS investigations showed that in all cases, the oxide scales compositions were substantially similar. The scale consisted of an outer layer built of Al₂O₃ with the presence of some amounts of TiO₂, an intermediate layer of the scale consisting of TiO₂, an inner layer composed of oxides and nitrides. Additionally, niobium rich particles at the scale/substrate interface were present. The oxidation mechanism of Ti–46Al–8Nb was studied via two-stage isothermal oxidation (24 h in ¹⁶O₂ followed by 24 h in ¹⁸O₂) at 1073 K combined with secondary neutral mass spectroscopy (SNMS). These results indicate that the oxidation mechanism depends on a mixed diffusion process, consisting of outward transport of cations and simultaneous oxygen inward transport.     

Analysis of the electrochemical reaction behavior of alloy AZ91 by EIS technique in H3PO4/KOH buffered K2SO4 solutions

The EIS technique was used to analyze the electrochemical reaction behavior of Alloy AZ91 in H₃PO₄/KOH buffered K₂SO₄ solution at pH 7. The corrosion resistance of Alloy AZ91 was directly related with the stability of Al₂O₃ · xH₂O rich part of the composite oxide/hydroxide layer on the alloy surface. The break down of the oxide layer was estimated to occur mainly on the matrix solid solution phase in Alloy AZ91. The mf capacitive loop arose from the relaxation of mass transport in the solid oxide phase in the presence of Al₂O₃ · xH₂O rich part and from Mg⁺ ion concentration within the broken area in the absence of Al₂O₃ · xH₂O rich part in the composite oxide structure on the alloy surface. The lf inductive loop had tendency of disappear when the dissolution rate of the alloy decreased as a result of the formation of the protective oxide layer.     

Effect of tin on high-temperature sulphidation of Fe-Cr alloys in H2/H2S atmospheres

The high temperature sulphidation behaviour of Fe-46Cr-xSn (x = 0; 0.2; 0.5; 1; 2) alloys has been studied at temperatures of 1073, 1173 and 1273 K in H₂/H₂S mixtures with different sulphur vapour partial pressures of 10⁻¹, 10⁻³ and 10⁻⁵ Pa. Thermogravimetric studies in combination with scanning electron microscope (SEM), with energy dispersive spectrometer (EDS), and X-ray diffraction (XRD) techniques, have displayed a significant influence of the sulphur partial pressure on the composition and growth rate of the sulphide scale. The results have shown that addition of tin increases the sulphidation rate of Fe-46Cr alloys but not considerably (except at temperatures of 1073 and 1173 K combined with sulphur partial pressure of 10⁻⁵ Pa). The metallic core of the studied samples was enriched in tin and iron, moreover tin was found in the internal layer close to the metallic core as metallic Fe_xSn_y inclusions with tin concentrations of up to 12 at.%.     

Oxidation inhibition of γ-TiAl alloy at 900 °C by inorganic silicate composite coatings

Inorganic silicate composite coatings on γ-TiAl were fabricated by air spraying. The oxidation behaviour of the alloy was investigated at 900 °C. The results indicated that rapid oxidation occurred in the γ-TiAl, and multilayered non-protective TiO₂ and Al₂O₃ scales formed. For coated γ-TiAl alloy, the oxidation was markedly inhibited; a thin Al₂O₃ layer was detected, which improved the oxidation resistance of the alloy. The low oxygen partial pressure at the interface of the coatings and the alloy promotes the preferentially oxidation of Al in the γ-TiAl substrate, and the outward diffusion of Ti to form TiO₂ was retarded.     

Enhanced sulphidation/oxidation resistance of Ti–45Al–8Nb alloy by multilayered coatings at 850°C for up to 675 h

The high temperature sulphidation/oxidation behaviour of three multilayered coatings CrAlYN/CrN etched by Y⁺, CrAlYN/CrN etched by Cr⁺ and CrAlYN/CrN etched CrAl⁺ and the uncoated γ-TiAl (Ti–45Al–8Nb (at-%) used as reference sample was studied at 850°C for 675 h. Sulphidation/oxidation test was performed in the environment of H₂/H₂S/H₂O, yielding pS₂?=?10^?1 Pa and pO₂?=?10^?18 Pa. Kinetic data obtained by discontinuous gravimetric method showed that the multilayered coatings effectively enhanced the sulphidation/oxidation resistance of γ-TiAl alloy. The corrosion resistance decreasing in order: CrAlYN/CrN etched by Y⁺>CrAlYN/CrN etched by CrAl⁺>CrAlYN/CrN etched by Cr⁺>γ-TiAl. Scale development studies using SEM, EDX and X-ray diffraction confirmed two regions of the coated materials: ‘affected,’ where coating cracked and developed non-protective TiO₂ scale, and ‘unaffected,’ where protective (Al,Cr)₂O₃ scale formed. The uncoated γ-TiAl material, after exposure, showed a typical multilayered structure consisting of layers of TiO₂ and Al₂O₃.     

Oxidation of a chromia-forming nickel base alloy at high temperature in mixed diluted CO/H2O atmospheres

Corrosion of a chromia-forming nickel base alloy, Haynes 230^®, has been investigated under impure helium containing a few Pa of CO and H₂O at 900 °C. It has been found that this alloy reacts simultaneously with CO and H₂O. Oxidation by CO has been revealed to occur mainly in the first hours. CO diffuses through the scale via short-circuit pathways and oxidizes Al, Cr and Si at the oxide/metal interface. Kinetics of CO oxidation has been investigated and several rate limiting steps are proposed. In the long term, H₂O is the major oxidant of chromia-forming nickel base alloys in impure helium.     

Synergistic corrosion behavior of coated Ti60 alloys with NaCl deposit in moist air at elevated temperature

In the present paper, the corrosion behavior of Ti60 alloys with an aluminide, TiAlCr, and enamel coatings in moist air containing NaCl vapor at 700-800 °C were studied. The results showed that the TiAlCr and aluminide coatings failed to protect the substrate from corrosion due to the cyclic formation of volatile products during corrosion at 800 °C. However, an uneven continuous protective Al₂O₃ scale could form on the aluminide coating during corrosion at 700 °C. And the enamel coating could protect Ti60 from corrosion due to its high thermochemical stability and matched thermal expansion coefficient with substrates of Ti-base alloys during corrosion.     

Corrosion resistance of TiO2 films grown on stainless steel by atomic layer deposition

Titanium dioxide (TiO₂) films have been deposited onto stainless steel substrates using atomic layer deposition (ALD) technique. Composition analysis shows that the films shield the substrates entirely. The TiO₂ films are amorphous in structure as characterized by X-ray diffraction. The electrochemical measurements show that the equilibrium corrosion potential positively shifts from − 0.96 eV for bare stainless steel to − 0.63 eV for TiO₂ coated stainless steel, and the corrosion current density decreases from 7.0 × 10^− 7 A/cm² to 6.3 × 10^− 8 A/cm². The corrosion resistance obtained by fitting the impedance spectra also reveals that the TiO₂ films provide good protection for stainless steel against corrosion in sodium chloride solution. The above results indicate that TiO₂ films deposited by ALD are effective in protecting stainless steel from corrosion.     

The nature of the third-element effect in the oxidation of Fe-xCr-3 at.% Al alloys in 1 atm O2 at 1000 °C

The oxidation of an Fe-Al alloy containing 3 at.% Al and of four ternary Fe-Cr-Al alloys with the same Al content plus 2, 3, 5 or 10 at.% Cr has been studied in 1 atm O₂ at 1000 °C. Both Fe-3Al and Fe-2Cr-3Al formed external iron-rich scales associated with an internal oxidation of Al or of Cr+Al. The addition of 3 at.% Cr to Fe-3Al was able to stop the internal oxidation of Al only on a fraction of the alloy surface covered by scales containing mixtures of the oxides of the three alloy components, but not beneath the iron-rich oxide nodules which covered the remaining alloy surface. Fe-5Cr-3Al formed very irregular external scales where areas covered by a thin protective oxide layer alternated with others covered by thick scales containing mixtures of the oxides of the three alloy components, undergrown by a thin layer rich in Cr and Al, while internal oxidation was completely absent. Conversely, Fe-10Cr-3Al formed very thin, slowly-growing external Al₂O₃scales, providing an example of third-element effect (TEE). However, the TEE due to the Cr addition to Fe-3Al was not directly associated with a prevention of the internal oxidation of Al, but rather with the inhibition of the growth of external scales containing iron oxides. This behavior has been interpreted on the basis of a qualitative oxidation map for ternary Fe-Cr-Al alloys taking into account the existence of a complete solid solubility between Cr₂O₃ and Al₂O₃.     

The corrosion of Fe3Al alloy in liquid zinc

A systematic study of the isothermal corrosion testing and microscopic examination of Fe₃Al alloy in liquid zinc containing small amounts of aluminum (less than 0.2 wt.%) at 450 °C was carried out in this work. The results showed the corrosion of Fe₃Al alloy in molten zinc was controlled by the dissolution mechanism. The alloy exhibited a regular corrosion layer, constituted of small metallic particles (diameter: 2-5 μm) separated by channels filled with liquid zinc, which represented a porosity of about 29%. The XRD result of the corrosion layer formed at the interface confirmed the presence of Zn and FeZn_6.67. The corrosion rate of Fe₃Al alloy in molten zinc was calculated to be approximately 1.5 × 10⁻⁷ g cm⁻² s⁻¹. Three steps could occur in the whole process: the superficial dissolution of metallic Cr in the corrosion layer, the new phase formation of FeZn_6.67 and the diffusion of the dissolved species in the channels of the corrosion 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.     

Characterization of the hot deformation behavior of a Ti-22Al-25Nb alloy using processing maps based on the Murty criterion

Isothermal compression testing of Ti-22Al-25Nb alloy was carried out at deformation temperatures between 940 and 1060 °C with strain rate between 0.001 and 10 s⁻¹, and a height reduction of 50%. The hot deformation behavior of Ti-22Al-25Nb alloy was characterized based on an analysis of the stress-strain behavior, kinetics and the processing map, for obtaining optimum processing windows and achieving desired microstructures during hot working. The constitutive equation was established, which described the flow stress as a function of the strain rate and deformation temperature. The apparent activation energies were calculated to be 788.77 kJ/mol in the α₂ + β/B2 + O phase region and 436.23 kJ/mol in the α₂ + B2 phase region, respectively. Based on Dynamic Material Model and the Murty instability criterion, the processing map for the Ti-22Al-25Nb alloy was constructed for strain of 0.6. The map exhibits a stable domain for the temperature range of 940-1060 °C and strain rate range of 0.001-0.1 s⁻¹ with two peaks in power dissipation of 51 and 56%, occurring at 940 °C/0.001 s⁻¹ and 1060 °C/0.001 s⁻¹, respectively. One is associated with lamellar globularization, and the other displays a phenomenon of recrystallization. Therefore, the desired processing condition of the Ti-22Al-25Nb alloy is 940 °C/0.001 s⁻¹ in the α₂ + β/B2 + O phase field. Moreover, the material also undergoes flow instabilities at strain rates higher than 1 s⁻¹. This instability domain exhibits flow localization and adiabatic shear bands which should be avoided during hot processing in order to obtain satisfactory properties.     

High-Temperature Corrosion of Ti–46Al–6Nb–0.5W–0.5Cr–0.3Si–0.1C Alloy in N2/0.1%H2S Gas

Ti–46Al–6Nb–0.5W–0.5Cr–0.3Si–0.1C alloy was corroded at 800–1100 °C for 200 h in N₂/0.1%H₂S gas to characterize its corrosion behavior in an aggressive H₂S-containing environment. The alloy displayed superior corrosion resistance because Ti and Al preferentially reacted with impurity oxygen in the gas to form TiO₂ and Al₂O₃. It corroded primarily by outward diffusion of Ti, Al, W, and Cr in addition to inward transport of sulfur, nitrogen, and oxygen. Scales were adherent and consisted of an outer TiO₂ layer, an intermediate Al₂O₃ layer, and an inner (TiO₂, Al₂O₃)-mixed layer. TiN and Ti₂AlN formed at the scale/matrix interface where sulfur, Nb, W, and Cr segregated.

     

Oxidation and tribological properties of anodized Ti45Al8.5Nb alloy

The oxidation performance and tribological properties of the anodized Ti45Al8.5Nb were investigated. Anodization was performed in ethylene glycol containing 0.15 mol/L NH₄F. Results showed that the anodized Ti45Al8.5Nb alloy exhibited good resistance against oxidation. After 100 h oxidation at 1000 °C, the mass gain of the anodized Ti45Al8.5Nb alloy was only 0.37 mg/cm². This is attributed to the generation of protective oxide scale. On the other hand, the hardness and elastic modulus of the anodized Ti45Al8.5Nb alloy decreased and then increased with the prolonging of thermal exposure due to the generation of the Al₂O₃-enriched outermost oxide layer.     

Prevention of passive film breakdown and corrosion of iron in 0.1 M KClO4 with and without Cl by covering with an ultrathin two-dimensional polymer coating and healing treatment in 0.1 M NaNO3

A two-dimensional polymer coating, the self-assembled monolayer of 16-hydroxy hexadecanoate ion HO(CH₂)₁₅ modified with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and octadecyltriethoxysilane C₁₈H₃₇Si(OC₂H₅)₃ was prepared on the passivated iron electrode and further, the passive film was healed by additional treatment in 0.1 M NaNO₃. This electrode was immersed in oxygenated 0.1 M KClO₄ solutions with and without 1 × 10⁻⁴ to 1 × 10⁻² M of Cl⁻. Protection of passive film against breakdown by covering the electrode with the polymer coating was examined by monitoring the open-circuit potential during immersion in the solutions for many hours to determine the time for passive film breakdown, t_bd. Repeated polarization measurements were carried out during immersion in these solutions for obtaining the protective efficiency, P. The t_bd value of the passivated, polymer-coated and healed electrode in 0.1 M KClO₄ solutions with and without Cl⁻ increased with a decrease in the concentration of Cl⁻. No breakdown occurred on the electrode during immersion in 0.1 M KClO₄ solutions with and without 1 × 10⁻⁴ of Cl⁻ for 360 h. The P values were extremely high, more than 99.9% before t_bd, indicating complete protection of iron from corrosion. The effect of healing treatment in 0.1 M NaNO₃ on passive film breakdown was investigated by electron-probe microanalysis.     

Subsurface microstructural changes in a cast heat resisting alloy caused by high temperature corrosion

A cast HP ModNb alloy (Fe-25Cr-35Ni-1Nb, wt.%) was oxidised and carburised in CO-CO₂ corresponding to a_C = 0.1 and p_O2 = 3 × 10⁻¹⁶ atm at 1080 °C. Formation of an external, chromium-rich oxide scale led to depletion of this metal in a deep alloy subsurface zone. Within that zone, secondary chromium-rich carbides dissolved, primary carbides oxidised, solute silicon and aluminium internally oxidised, and extensive porosity developed. Pore volumes correspond to the difference between metal loss by scaling and metal displacement by internal oxidation, assuming the scale-metal interface to be fixed. The pores are concluded to be Kirkendall voids.     

Influence of oxygen ion irradiation on the corrosion aspects of Ti-5%Ta-2%Nb alloy and oxide coated titanium

The corrosion resistance of Ti-5%Ta-2%Nb alloy and DOCTOR (double oxide coating on titanium for reconditioning) coated titanium by O⁵⁺ ion irradiation were compared and investigated for their corrosion behaviour. O⁵⁺ ion irradiations were carried out at a dose rate of 1 × 10¹⁷, 1 × 10¹⁸ and 1 × 10¹⁹ ions/m² at 116 MeV. The surface properties and corrosion resistance were evaluated by using scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive X-ray (EDX), glancing-angle X-ray diffraction (GXRD) and electrochemical testing methods. The results of electrochemical investigations in 11.5 N HNO₃ indicated that the open circuit potential (OCP) of DOCTOR coated titanium is nobler than Ti-5%Ta-2%Nb alloy. The potentiodynamic polarization study of Ti-5%Ta-2%Nb alloy and DOCTOR coated specimen indicated decrease in passive current density with increase in ion doses (1 × 10¹⁷ to 1 × 10¹⁹ ions/m²) indicating decrease in anodic dissolution. Nyquist arc behaviour in the electrochemical impedance study substantiated the enhancement in oxide layer stability by O⁵⁺ ion irradiation. AFM results revealed that the DOCTOR coated Ti surface was dense without gross voids, and the surface roughness decreased by O⁵⁺ ion irradiation, but increased after corrosion test. EDX and GXRD patterns of DOCTOR coated Ti sample indicated that the coating was mainly composed of rutile TiO₂. Based on the above results, the O⁵⁺ ion irradiation effect on corrosion behavior of Ti-5%Ta-2%Nb alloy and DOCTOR coated titanium are discussed in this paper.     

Effect of RF deposition power on the properties of Al-doped TiO2 thin films

The Al-doped TiO₂ (TiO₂:Al) films were deposited by simultaneous RF (Radio Frequency) magnetron sputtering of TiO₂ and DC (Direct Current) magnetron sputtering of Al. The advantage of this method is that the Al content could be independently controlled. TiO was more favorable to form and the deposited films became nonstoichiometric by increasing RF power density. The morphologies of TiO₂ and TiO₂:Al films were significantly affected by RF power density. The nonlinear refractive index of TiO₂:Al film on the glass substrate was measured by Moiré deflectometry, and was of the order of 10^− 8 cm² W^− 1. Compared with TiO₂ film, TiO₂:Al film had smaller grain size, lower porosity, higher linear refractive index, lower stress-optical coefficient and higher VIS-IR transmission.