Microstructure evolution and mechanical properties of GH984G alloy with different Ti/Al ratios during long-term thermal exposure

GH984G alloy is a low cost Ni–Fe based wrought superalloy designed for 700 °C advanced ultra-supercritical (A-USC) coal-fired power plants. In this paper, the microstructure evolution and tensile properties of GH984G alloy with different Ti/Al ratios during thermal exposure at different high temperatures are investigated. Detailed microstructure analysis reveals that the Microstructure of alloys with different Ti/Al ratios are similar after standard heat treatment, and the primary precipitates are γ′, MC, M₂₃C₆ and M₂B. However, η phase precipitates at grain boundary in the alloy with high Ti/Al ratio after thermal exposure at 750 °C for 570 h. By contrast, the microstructure stability of the alloy with lower Ti/Al ratio is excellent. There is no detrimental phase even if after thermal exposure at 750 °C for 5000 h in the alloy with lower Ti/Al ratio. γ′ coarsening plays a great role on the tensile strength, and the critical size range of γ′ could be defined as approximately 27–40 nm. The influence of η phase on tensile strength has close relationship with its volume fraction, the high volume fraction results in the decrease of tensile strength. The tensile strength of the alloy with lower Ti/Al ratio is obviously higher than the alloy with higher Ti/Al ratio and the yield strength has no obvious decrease during long-term thermal exposure at 700 °C. It is demonstrated that the thermal stability of microstructure and mechanical properties of GH984G alloy can be improved by moderately decreasing Ti/Al ratio to satisfy the requirement of A-USC plants.     

The isothermal and cyclic oxidation behaviour of Ti-48Al-2Cr at 700°C

The effect of the microstructure on the isothermal and cyclic oxidation behaviour of the intermetallic Ti–48A1–2Cr (at.%) alloy was investigated at 700°C in air up to 3000 h. Different microstructures, i.e., duplex, near gamma, nearly lamellar, and fully lamellar, obtained by various heat treatments, were used. Results of thermogravimetry showed a good oxidation resistance at 700°C against both isothermal and cyclic oxidation. The growth rate of the oxide scale, as well as its composition, structure and morphology showed no major relation to the microstructure of the base material. After equal exposure times, cyclic oxidation induced a higher oxidation rate compared to isothermal oxidation. Oxidation of Ti–48A1–2Cr in air, initially resulted in the formation of α-A1₂O₃, TiO₂ (rutile), Ti₂A1N and TiN, with the latter two near the scale/substrate interface. After longer exposure times, the mixed corrosion scale was overgrown by fast growing TiO₂. The oxide scales, formed under isothermal as well as under cyclic conditions, were uniform.     

Isothermal oxidation behavior of the TZAV-20 alloy

Oxidation behavior is important for secure and long-life service of metals and alloys. The isothermal oxidation behavior of the Ti–20Zr–6.5Al–4V alloy at 470 to 670 °C was investigated. The kinetics analysis shows that the oxidation of TZAV-20 alloy below 570 °C accords with the parabolic law. While the alloy oxidized at 670 °C, obeys the linear law. As oxidation temperature increases from 470 to 670 °C, the oxidation products change as: TiO₂ → TiO₂ + ZrO₂ → TiO₂ + ZrO₂ + Al₂O₃. Relation between weight gain and thickness of oxidation film shows that the weight will increase 0.171 mg/cm² for every 1 μm increasing in thickness. The surface hardness increases from approximately 380 HV for base material to 689 HV for 670 °C oxidized specimen. In short, the TZAV-20 alloy has favorable inoxidizability below 570 °C. The findings will not only promote practical applications of the new TiZrAlV series alloys but also supplement the oxidation theory.     

Characterization of chromia scales formed in supercritical carbon dioxide

Abstract

Initial experimental work at 700°–800 °C is in progress to develop a lifetime model for supercritical CO₂ (sCO₂) compatibility for a 30-year lifetime of a >700 °C concentrated solar power system. Nickel-based alloys 282, 740H and 625 and Fe-based alloy 25 are being evaluated in 500-h cycles at 1 and 300 bar, and 10-h cycles in 1 bar industrial grade CO₂. The alloys showed similar low rates of oxidation in 1 and 300 bar CO₂ in 500-h cycles at 750 °C. However, in 10-h cycles, alloy 25 showed accelerated attack at 700° and 750 °C. Transmission electron microscopy scale cross-sections on alloy 25 after 1000 h at 700 °C in sCO₂ and in air only showed a small row of carbides beneath the scale in the former environment. Similar characterisation was performed on alloys 625 and 282 after sCO₂ exposure at 750 °C.     

Investigation and improvement on structural stability and stress rupture properties of a Ni–Fe based alloy

The structural stability and stress rupture properties of a Ni–Fe based alloy, considered as boiler materials in 700 °C advanced ultra-supercritical (A-USC) coal-fired power plants, was studied. Investigation on the structural stability of the existing alloy GH984 shows that the most important changes in the alloys are γʹ coarsening, the γʹ to η transformation and the coarsening and agglomeration of grain boundary M₂₃C₆ during thermal exposure. The stress rupture strength was found to be slightly lower than the requirement of 700 °C A-USC. The fracture mode of creep tested specimens was intergranular fracture. Detailed analysis revealed that η phase precipitation is sensitive to Ti/Al ratio and can be suppressed by decreasing Ti/Al ratio. The coarsening behavior of γʹ phase is related to Fe content. Adding B and P was suggested to stabilize M₂₃C₆ and increase grain boundary strength. Based on the research presented and analysis of the data, a modified alloy was developed through changes in composition. For the modified alloy, η phase is not observed and M₂₃C₆ is still blocky and discretely distributes along grain boundary after thermal exposure at 700 °C for 20,000 h. Moreover, the creep strength is comparable to the levels of Ni-based candidate alloys for 700 °C A-USC.     

Evolution of oxide scale on a Ni–Mo–Cr alloy at 900 °C

The cyclic oxidation behavior of a Ni–Mo–Cr alloy was studied in air at 900 °C for exposure periods of up to 1000 h. The morphology, microstructure and composition of the oxide scale was characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy and X-ray diffraction. Oxidation kinetics was determined by weight gain measurements. The results show that steady state oxidation was achieved within 1 h of exposure. During transient oxidation, the alloy grain boundaries intersecting the alloy surface became depleted in Ni and enriched in Mo and Cr. The scale initially formed at the surface was NiO which grew outwardly. However, a protective Cr₂O₃ layer developed, rapidly retarding the rate of oxidation. Formation of NiMoO₄ was also observed. The presence of Mo in the alloy facilitated the formation of a Cr₂O₃ layer at an early stage of oxidation. The alloy exhibited considerable oxide spalling during prolonged exposure.     

Fabrication of thin film TiO2 nanotube arrays on Co–28Cr–6Mo alloy by anodization

Titanium oxide (TiO₂) nanotube arrays were prepared by anodization of Ti/Au/Ti trilayer thin film DC sputtered onto forged and cast Co–28Cr–6Mo alloy substrate at 400 °C. Two different types of deposited film structures (Ti/Au/Ti trilayer and Ti monolayer), and two deposition temperatures (room temperature and 400 °C) were compared in this work. The concentrations of ammonium fluoride (NH₄F) and H₂O in glycerol electrolyte were varied to study their effect on the formation of TiO₂ nanotube arrays on a forged and cast Co–28Cr–6Mo alloy. The results show that Ti/Au/Ti trilayer thin film and elevated temperature sputtered films are favorable for the formation of well-ordered nanotube arrays. The optimized electrolyte concentration for the growth of TiO₂ nanotube arrays on forged and cast Co–28Cr–6Mo alloy was obtained. This work contains meaningful results for the application of a TiO₂ nanotube coating to a CoCr alloy implant for potential next-generation orthopedic implant surface coatings with improved osseointegrative capabilities.     

Improvement of high-temperature oxidation resistance of titanium-based alloy by sol–gel method

Sol–gel dip coating of SiO₂ was applied on a TiAl-based alloy, and subsequent heat treatment was performed. XRD and SEM/EDS analysis revealed that an amorphous silica coating was formed on the alloy. Isothermal oxidation and cyclic oxidation at 600 and 700 °C in static air of the specimens with or without coating were performed to investigate the effect of the SiO₂ coating on the oxidation behavior of the alloy by thermogravimetry. The average parabolic rate constants of the coated specimens were greatly reduced due to the presence of the coating. Severe cracks and spallation of the scales were observed on the blank specimens, but not on the coated ones. The oxide scales formed on the uncoated specimens were stratified. For the coated samples, a mixture layer of rutile TiO₂ and Al₂O₃ occurred beneath the applied film.     

High-energy ball milling of intermetallic Ti-Cu alloys for the preparation of oxide nanoparticles

Copper and titanium oxides in the nano-size range show unique chemical and physical properties and thus have been intensively considered for novel and smart applications. In this work, oxide nanoparticles were prepared by high-energy ball milling of Ti-Cu alloys followed by a controlled oxidation process. Alloys of the Ti-Cu system Ti-50Cu, Ti-57Cu, and Ti-65Cu (in wt.%) prepared by arc melting were selected considering they provide different starting brittle intermetallic phases before milling. Microstructural investigation indicated that Ti-50Cu was composed of Ti₂Cu and TiCu, while Ti-57Cu was single-phase TiCu. Ti-65Cu was dual-phase and consisted of Ti₃Cu₄ and Ti₂Cu_3. A mean particle size below 10 nm was achieved after high-energy ball milling for all compositions. The oxidation process was then investigated in two temperature ranges. At high oxidation temperatures of 700–800 °C, a complete oxidation took place leading to oxides TiO₂-rutile and CuO in all alloys. However, at a low oxidation temperature (350 °C), partial oxidation occurred and different oxides were obtained. Ti-50Cu was the most promising alloy and led to a mix of TiO₂ (rutile and anatase), CuO, Cu₂O, and Ti₃Cu₃O. After long exposure to thermal oxidation, the resulting oxides remained in the nanometric range with a particle size distribution showing a D50 of approximately 6 nm.     

Effect of aging on the tensile properties and microstructures of a near-alpha titanium alloy

The effect of aging temperature between 650 °C and 750 °C for different aging times on the tensile properties and microstructures of Ti60 alloy were studied. The results show that the strength of the alloy increases first and then decreases with the aging temperature increases from 650 °C to 750 °C. The reduction of area of the alloy is more sensitive to the aging time than elongation. With increasing aging temperature and time, the volume fracture and grain size of silicides and α₂ phase increase gradually. The silicides have the strengthen effect on the Ti60 alloy, but the effect weakens when the silicides grow up. The loss of ductility is mainly attributed to the precipitation of α₂ phase after aging treatment.     

High temperature oxidation of Ni2AlTi

The isothermal oxidation process in bulk and powdered Ni₂AlTi (L2₁ structure) has been studied in the temperature range of 600 to 1200° C in air by means of X-ray diffraction and scanning electron microscopy. At 900 and 1200° C, the transient oxides, NiO and TiO₂ were formed in the initial stage on the outer surface. Subsequent oxidation was dominated by outward diffusion of aluminium, resulting in the formation of a Ni₃Ti layer beneath an internal precipitation layer containing Al₂O₃-NiAl₂O₄ aggregates, NiTiO₃ and Ni₃Ti. Formation of NiTiO₃ and NiAl₂O₄ at the expense of NiO, TiO₂ and Al₂O₃ indicated the reaction among constituent oxides also occurred in the late stage of oxidation at 900 and 1200° C. Only NiO and TiO₂ were identified in specimens oxidized at 600° C up to 24h. The oxidation rate of Ni₂AlTi is of the same order of magnitude as the dilute γ-NiAl alloy at 1200° C.     

Oxidation behaviour of titanium-containing brazing filler metals

Brazements on alumina or partially stabilized zirconia (PSZ) of four silver- or copper-based brazing filler metals that contain titanium to promote wetting of and adherence to structural ceramics, were exposed in a thermogravimetric analyser at temperatures up to 700°C to atmospheres of 100% O₂, Ar-20% O₂ and Ar-3 p.p.m. O₂. The alloys included Cu-41.1Ag-3.6Sn-7.2Ti, Ag-44.4Cu-8.4Sn-0.9Ti, Ag-41.6Cu-9.7Sn-5.0Ti and Ag-37.4Cu-10.8In-1,4Ti, at%. All formed external oxides that were more or less protective under all of the test conditions studied. The growth of the oxides followed a parabolic time law. The gains in weight due to oxidation observed were small, ranging (for 45 h exposure at 400 °C to Ar-20% O₂) from 0.20 mgcm⁻² for the Ag-37.4Cu-10.8In-1.4Ti alloy to 0.46 mgcm⁻² for Cu-41.1Ag-3.6Sn-7.2Ti. As expected, weight gain increased with increasing temperature or . Unexpectedly, the titanium played a minor role in the scale formed on any of the filler metals with a titanium oxide, TiO₂, being found on only one alloy — Ag-41.6Cu-9.7Sn-5.0Ti. The brazements on PSZ gained weight at a higher rate than comparative brazements on alumina. We attribute this behaviour to oxygen transport through the zirconia resulting in the growth of an interfacial layer of titanium oxide.     

Oxidation behavior of a new Fe–Ni–Cr-based alloy in pure steam at 750 °C

The isothermal oxidation of a new Fe–Ni–Cr-based alloy has been investigated in pure steam at 750 °C for exposure time up to 500 h using secondary electron microscope (SEM)/ X-ray energy-dispersive spectroscopy (EDS) and X-ray diffraction (XRD). Results showed that the alloy was oxidized approximately following a parabolic law with a parabolic rate constant k_p of 2.36 × 10^?13 g²/m⁴/s. As revealed by SEM/EDS and XRD results, a duplex-layered external oxide scale was formed, consisting of a thin outer layer of Ni(Fe, Al)₂O₄ and a thicker inner layer of (Cr, Mn)₂O₃. Underneath the external oxide scale, the internal oxidation of Ti to be TiO₂ occurred particularly along the grain boundaries of the matrix alloy. Internal oxide of Al₂O₃ was also observed but at a deeper depth. Based on the detailed compositional and microstructural characterization of the oxidized zone, the mechanism of the external and internal oxidation in steam is presented.     

Influence of sol–gel derived Al2O3 film on the oxidation behavior of a Ti3Al based alloy

Al₂O₃ thin films were deposited on a Ti₃Al based alloy (Ti–24Al–14Nb–3V–0.5Mo–0.3Si) by sol–gel processing. Isothermal oxidation at temperatures of 900–1000 °C and cyclic oxidation at 800–900 °C were performed to test their effect on the oxidation behavior of the alloy. Results of the oxidation tests show that the oxidation parabolic rate constants of the alloy were reduced due to the applied thin film. This beneficial effect became weaker after longer oxidation time at 1000 °C. TiO₂ and Al₂O₃ were the main phases formed on the alloy. The thin film could promote the growth of Al₂O₃, causing an increase of the Al₂O₃ content in the composite oxides, sequentially decreased the oxidation rate. Nb/Al enriched as a layer in the alloy adjacent to the oxide/alloy interface in both the coated and uncoated alloy. The coated thin film decreased the thickness of the Nb/Al enrichment layer by reducing the scale growth rate.     

The kinetics of oxidation of diffusion coatings in superheated steam

Abstract

The kinetics of oxidation of Cr-rich, Si–Cr-rich and Al-Cr-rich diffusion layers have been studied in superheated steam within the temperature range 650 and 750°C. The diffusion layers were generated in test-pieces of alloy type P-92 using the pack cementation approach. The thermogravimetric analytical technique was used to determine the kinetic in superheated steam over a period of 100 h. The results were benchmarked against the oxidation kinetic of the bare P92 alloy at 650°C. The results of these short-term experiments indicated a significant improvement in oxidation resistance where the diffusion layers did not experience any apparent attack. The oxidation kinetics of a test-piece of alloy type S304H were also determined at 750°C. The latter type of samples experienced oxidation with the formation of a 1 μm thick Fe–Cr spinel type oxide with discrete patches of break-away oxidation. By comparison the diffusion layers showed no apparent attack. The diffusion layer chemistry remained stable even at 750°C for all coated composition. The characteristics of the diffusion layers will be presented.     

Effect of Mo-alloyed layer on oxidation behavior of TiAl-based alloy

A Mo-alloyed layer was prepared on a TiAl-based alloy using plasma surface metallurgy technique. The microstructure and oxidation behavior of the alloyed TiAl were investigated. The surface alloyed layer with a thickness of approx. 40 μm and a gradient concentration distribution was composed of Ti₂MoAl, TiAl and Mo phases. Cycling oxidation test was carried out at 850 °C in air under an atmospheric pressure. The result of the oxidation kinetics test shows that the mass gain of the Mo-alloyed TiAl after exposure for 100 h was less than the value of the untreated TiAl substrate, exhibiting an improved oxidation resistance. The Al₂O₃-rich mixed oxide scale formed on the alloyed TiAl is supposed to be the main reason of the beneficial effect on the improvement of oxidation resistance for TiAl-based alloy.     

Effect of minute element addition on the oxidation resistance of FeCoCrNiAl and FeCoCrNi2Al high entropy alloy

The effect of Ti_0.1 and Ti_0.1Si_0.1 addition on the high temperature isothermal oxidation behavior of dense FeCoCrNiAl and FeCoCrNi₂Al high entropy alloy (HEA) consolidated by vacuum hot pressing were investigated by X-ray diffraction, Scanning Electron Microscopy and Raman Spectroscopy. Mechanical properties such as hardness, Young’s modulus, and thermal properties such as differential scanning calorimetry (DSC) and coefficient of thermal expansion (CTE) were also investigated. The weight gain recorded after isothermal oxidation for 5,25,50 and 100 h at 1050 °C was found to be parabolic in nature. X-ray diffraction analysis (XRD), as well as Raman spectroscopy analysis of HEA’s oxidized at 1050 °C for 100 h, shows the formation of the Al₂O₃ phase. A homogeneous thin oxide scale without any discontinuity was observed throughout the cross-section. Ti and Si addition in 0.1 at. % improves mechanical properties, oxidation resistance, and reduces waviness of the oxide scale.     

Effect of microalloying with silicon on high temperature oxidation resistance of novel refractory high-entropy alloy Ta-Mo-Cr-Ti-Al

Abstract

The effect of 1 at.% Si addition to the refractory high-entropy alloy (HEA) Ta–Mo–Cr–Ti–Al on the high temperature oxidation resistance in air between 900 °C and 1100 °C was studied. Due to the formation of protective chromia-rich and alumina scales, the thermogravimetric curves for Ta–Mo–Cr–Ti–Al and Ta–Mo–Cr–Ti–Al–1Si showed small mass changes and low oxidation rates which are on the level of chromia-forming alloys. The oxide scales formed on both alloys at all temperatures are complex and consist of outermost TiO₂, intermediate Al₂O₃, and (Cr, Ta, Ti)-rich oxide at the interface oxide/substrate. The Si addition had a slightly detrimental effect on the oxidation resistance at all temperatures primarily as a result of increased internal corrosion attack observed in the Si-containing HEA. Large Laves phase particles distinctly found in the Si-containing alloy were identified to be responsible for the more rapid internal corrosion.     

Creep behavior of INCOLOY alloy 617

The microstructural features of INCOLOY alloy 617 in the solution annealed condition and after long-term creep tests at 700 and 800 °C were characterized and correlated with hardness and creep strength. Major precipitates included (Cr,Mo,Fe)₂₃C₆ carbides and the δ-Ni₃Mo phase. M₆C and MC carbides were also detected within the austenitic grains. However, minor precipitates particularly γ′-Ni₃(Al,Ti) was found to play an important role. At different exposure temperatures, the microstructural features of the Ni–22Cr–12Co–9Mo alloy changed compared with the as-received condition. The presence of discontinuously precipitated (Cr,Mo,Fe)₂₃C₆ carbides and their coarsening until the formation of an intergranular film morphology could be responsible both for a reduction in rupture strength and for enhanced intergranular embrittlement. The fraction and morphology of the γ′-phase, precipitated during exposure to high temperature, also changed after 700 or 800 °C exposure. At the latter test temperature, a lower volume fraction of coarsened and more cubic γ′ precipitates were observed. These microstructural modifications, together with the presence of the δ-phase, detected only in specimens exposed to 700 °C, were clearly responsible for the substantially good creep response observed at 700 °C, compared with that found at 800 °C.     

Oxidation behaviour of TiAlYN/CrN and CrAlYN/CrN nanoscale multilayer coatings with Al2O3 topcoat deposited on γ-TiAl alloys

Abstract

TiAlYN/CrN and CrAlYN/CrN nanoscale multilayer coatings were deposited on γ-TiAl specimens using magnetron sputtering techniques. The nitride layers were manufactured by unbalanced magnetron sputtering (UBM) and high power impulse magnetron sputtering (HIPIMS). The CrAlYN/CrN coatings had an oxy-nitride overcoat. On some of the coated samples an additional alumina topcoat was deposited. The oxidation behaviour of the different coatings was investigated at 750 and 850°C performing quasi-isothermal oxidation tests in laboratory air. Mass change data were measured during exposure up to failure or the maximum exposure length of 2500 h. When exposed to air at 750°C, the Ti-based nitride films exhibited higher oxidation resistance than the Ti – 45Al –8Nb substrate material. The alumina topcoat enhanced the oxidation protection of this coating system, acting as diffusion barrier to oxygen penetration. At 850°C, the TiAlYN/CrN films exhibited poor stability and rapidly oxidised, and therefore were not applicable for long-term protective coatings on γ-TiAl alloys. The beneficial effect of the additional Al₂O₃ layer was less pronounced at this exposure temperature. The Cr-based nitride films exhibited high oxidation resistance during exposure at 850°C. HIPIMS deposition improved the oxidation behaviour of the CrAlYN/CrN nanoscale multilayer coatings in comparison to UBM coatings. For these coatings, the decomposed and partially oxidised nitride films were an effective barrier to oxygen inward diffusion. The alumina topcoat did not significantly increase the oxidation resistance of the γ-TiAl alloy coated with Cr-based nitride films.