Microstructural evolution during high-temperature oxidation of Ti2AlC ceramics

Microstructural development during high-temperature oxidation of Ti₂AlC below 1300 °C involves gradual formation of an outer discontinuous TiO₂ layer and an inner dense and continuous α-Al₂O₃ layer. After heating at 1400 °C, an outer layer of mixed TiO₂ and Al₂TiO₅ phases and a cracked α-Al₂O₃ inner layer were formed. After heating to 1200 °C and cooling to room temperature, two types of planar defect were identified in surface TiO₂ grains: twins with (2 0 0) twin planes, and stacking faults bounded by partial dislocations. Formation of planar defects released the thermal stresses that had generated in TiO₂ grains due to thermal expansion mismatch of the phases (TiO₂, α-Al₂O₃ and Al₂TiO₅) in the oxide scale. After heating to 1400 °C and cooling to room temperature, crack propagation in TiO₂ grains resulted from the thermal expansion mismatch of the phases in the oxide scale, the high anisotropy of thermal expansion in Al₂TiO₅ and the volume changes associated with the reactions during Ti₂AlC oxidation. An atomistic oxidation mechanism is proposed, in which the growth of oxide scale is caused by inward diffusion of O^2? and outward diffusion of Al³⁺ and Ti⁴⁺. The weakly bound Al leaves the Al atom plane in the layered structure of Ti₂AlC, and diffuses outward to form a protective inner α-Al₂O₃ layer between 1100 and 1300 °C. However, the α-Al₂O₃ layer becomes cracked at 1400 °C, providing channels for rapid ingress of oxygen to the body, leading to severe oxidation.     

The effect of fe on high temperature oxidation of NiAl

A study was conducted to observe the oxidation of NiAl+3.5at.%Fe alloy inβ-NiAl phase field at air temperatures of 1000, 1200 and 1400°C, and these results were compared with those of pure NiAl alloys. The primary effects of the Fe-addition in NiAl were found to be: 1) decrease in oxidation resistance and adherence of scales during both isothermal and cyclic oxidation tests, 2) enhancement of phase transformation rate from θ toα-AL₂O₃, 3) more rapid formation of characteristically ridgedα-A1₂O₃ scales during initial oxidation stages, and 4) partial sealing of voids formed at the scale-substrate interface and dissolution of Fe inside the alumina scale by the outward diffusion of Fe from the substrate alloy.     

Carburization Behavior of Electrodeposited Ni3 Al–CeO2-Base Coatings on Fe–Ni–Cr Alloys

The cyclic carburization of electrodeposited pure and CeO₂-dispersed Ni₃Al intermetallic coatings on Fe–Ni–Cr alloys has been investigated at 850 and 1050°C for periods up to 500 h in a reducing 2%CH₄–H₂ atmosphere. At 850°C, all Ni₃Al-base-coating samples showed excellent carburization resistance and slow mass increases due to the formation of a thin γ-Al₂O₃ scale and a low carbon activity (a _c = 0.73). At 1050°C and a high carbon activity (a _c = 3.21), all coatings are superior to the uncoated Fe–Ni–Cr alloy in terms of carburization resistance. A thin α-Al₂O₃ scale slowly formed on all Ni₃Al coatings effectively blocked the carbon attack. The addition of CeO₂ particles in the Ni₃Al coatings significantly mitigated the cracking of the α-Al₂O₃ scale and the resultant internal oxidation and carburization. For all coatings, Ni-rich particles were found to be formed on the α-Al₂O₃ scale during oxidation, which had led to the deposition of catalytic coke.     

Oxidation of Ti2AlC bulk and spray deposited coatings

The oxidation behaviour of Ti₂AlC bulk and high velocity oxy-fuel spray deposited coatings has been investigated for temperatures up to 1200 °C. X-ray diffraction and electron microscopy show that bulk Ti₂AlC forms a continuous layer of α-Al₂O₃ below a layer of TiO₂ at temperatures as low as 700 °C. Oxidation of the Ti₂AlC coatings is more complex, and also involves the phases Ti₃AlC₂, TiC, and Ti_xAl_y, formed during the spraying process. α-Al₂O₃ is observed, however, it is unevenly distributed deep into the material, and does not form a continuous layer essential for good oxidation resistance.     

Ultra-High-Temperature Oxidation and Thermal Stability of Ti<Subscript>2</Subscript>AlC in Air at 1600–1800 °C

The oxidation resistance and thermal stability of Ti₂AlC at 1600–1800 °C in air were studied by using induction heating method. The results showed that Ti₂AlC could survive with relatively low oxidation rate at temperatures up to 1650 °C for a short period of time due to the formation of an Al₂O₃ inner layer with certain protectiveness. However, at 1700 and 1800 °C, severe oxidation of Ti₂AlC happened, the entire Al₂O₃ inner layer no longer existed, and the whole oxide scale became porous, cracked and voluminous. In the oxidation processes, the Ti₂AlC substrate decomposed to TiC_x at 1700 °C, and transformed to Ti₃AlC₂ due to the reaction with TiC_x at 1800 °C, indicating that the massive consumption of Al in Ti₂AlC exceeded its deficiency tolerance.     

High-Temperature Oxidation Behavior of Ti2AlC in Air

The isothermal oxidation behavior of bulk Ti₂AlC in air has been investigated in temperature range 1000–1300°C for exposure time up to 20 hr by TGA, XRD, and SEM/EDS. The results demonstrated that Ti₂AlC had excellent oxidation resistance. The oxidation of Ti₂AlC obeyed a cubic law with cubic rate constants, k_c, increasing from 2.38×10^-12 to 2.13×10^-10 kg³/m⁶/sec as the temperature increased from 1000 to 1300°C. As revealed by X-ray diffraction (XRD) and SEM/EDS results, scales consisting of a continuous inner -Al₂O₃ layer and a discontinuous outer TiO₂ (rutile) layer formed on the Ti₂AlC substrate. A possible mechanism for the selective oxidation of Al to form protective alumina is proposed in comparison with the oxidation of Ti–Al alloys. In addition, the scales had good adhesion to the Ti₂AlC substrate during thermal cycling.     

Oxidation behavior of Ti3AlC2 at 1000-1400 °C in air

The isothermal oxidation behavior of bulk Ti₃AlC₂ has been investigated at 1000-1400 °C in air for exposure times up to 20 h by means of TGA, XRD, SEM and EDS. It has been demonstrated that Ti₃AlC₂ has excellent oxidation resistance. The oxidation of Ti₃AlC₂ generally followed a parabolic rate law with parabolic rate constants, k_p that increased from 4.1×10⁻¹¹ to 1.7×10⁻⁸ kg² m⁻⁴ s⁻¹ as the temperature increased from 1000 to 1400 °C. The scales formed at temperatures below 1300 °C were dense, adherent, resistant to cyclic oxidation and layered. The inner layer of these scales formed at temperatures below 1300 °C was continuous α-Al₂O₃. The outer layer changed from rutile TiO₂ at temperatures below 1200 °C to a mixture of Al₂TiO₅ and TiO₂ at 1300 °C. In the samples oxidized at 1400 °C, the scale consisted of a mixture of Al₂TiO₅ and, predominantly, α-Al₂O₃, while the adhesion of the scales to the substrates was less than that at the lower temperatures. Effect of carbon monoxide at scale/substrate was involved in the formation of the continuous Al₂O₃ layers.     

Effect of SI Content on the Oxidation Resistance of Ti3Al1-x Si x C2 (x⩽ 0.25) Solid Solutions at 1000–1400°C in Air

The oxidation behavior of Ti₃Al_1-x Si _x C₂ (x ⩽ 0.25) solid solutions was investigated in flowing air at 1000–1400°C for up to 20 hrs. Similar to Ti₃AlC₂, Ti₃Al_1-x Si _x C₂ (x⩽ 0.15) solid solutions display excellent oxidation resistance at all temperatures because of the formation of the continuous α-Al₂O₃ protective layers. However, Al₂(SiO₄)O formed during oxidation of Ti₃Al_1-x Si _x C₂ (x=0.2 and 0.25) solid solutions at and above 1100°C, which is believed to be responsible for the deterioration of oxidation resistance of Ti₃Al_0.75Si_0.25C₂ at 1300°C. Additionally, Ti₅Si₃ was also found in the oxidized samples. This implies that Ti₅Si₃ precipitated from Ti₃Al_1-x Si _x C₂ solid solutions during oxidation. But it has been proven that Ti₅Si₃ has little effect on the oxidation resistance of the material, which is attributed to an interstitial carbon effect.     

Oxidation Resistance of a Cr0.50Al0.50N Coating Prepared by Magnetron Sputtering on Alloy K38G

A Cr_0.50Al_0.50N coating has been prepared by a reactive-magnetron-sputtering method on alloy K38G. The coating possesses mainly the B1 type with a small amount of B4-type crystal structure phase. Isothermal oxidation tests were performed at 900–1,100 °C for 20 h by thermogravimetric analysis (TGA) in air. The results reveal that the coated samples have much lower mass gain than that of the bare alloy. The parabolic rate constants of the coated samples decrease by 2 orders of magnitude compared with the bare alloy at 1,000 and 1,100 °C. During the oxidation of the coated samples below 1,000 °C, the main oxide is Cr₂O₃, but above 1,000 °C, the scale changes to α-Al₂O₃. The observed oxidation behaviors demonstrate that the Cr_0.50Al_0.50N coating can provide good protection against corrosion over a wide temperature range.     

Effect of Y<Subscript>2</Subscript>O<Subscript>3</Subscript> content on the oxidation behavior of Fe-Cr-Al-based ODS alloys

A study was conducted to investigate the cyclic oxidation behavior of two oxide dispersion strengthened (ODS) Fe-Cr-Al based alloys containing 0.17 wt.% and 0.7 wt.% Y₂O₃. The alloys were oxidized in air for 100 h at 1200°C based on a 24 h cycle period. X-ray diffraction (XRD) and analytical transmission electron microscopy (TEM) were used to characterize the structure, morphology, and composition of the oxide scales. Both alloys formed highly adherent and continuous layers of α-Al₂O₃ exhibiting a morphology indicative of inward scale growth. The role of Y₂O₃ was to promote adherence by segregating to the grain boundaries within the oxide. Concurrently, Y₂O₃ generated micro-porosity resulting in a scale of comparatively higher thickness in the alloy with 0.7 wt.% Y₂O₃.     

High-temperature oxidation behavior of pure Ni3Al

The high-temperature oxidation behaviour of pure Ni₃Al alloys in air was studied above 1000°C. In isothermal oxidation tests between 1000 and 1200°C, Ni₃Al showed parabolic oxidation behavior and displayed excellent oxidation resistance. In cyclic oxidation tests between 1000 and 1300°C, Ni₃Al exhibited excellent oxidation resistance between 1000 and 1200°C, but drastic spalling of oxide scales was observed at 1300°C. When Ni₃Al was oxidized at 1000°C, Al₂O₃ was present as -Al₂O₃ in a whisker form. But, at 1100°C the gradual transformation of initially formed metastable -Al₂O₃ to stable -Al₂O₃ was observed after oxidation for about 20 hr. After oxidation at 1200°C for long times, the formation of a thick columnar-grain layer of -Al₂O₃ was observed beneath a thin and fine-grain outer layer of -Al₃O₃. The oxidation mechanism of pure Ni₃Al is described.     

Long-Time Oxidation of Cr2AlC Between 700 and 1,000?°C in Air

Cr₂AlC compounds were synthesized via a powder metallurgical route and their long-term oxidation behavior studied. Oxidation at temperatures between 700 and 1,000?°C for up to 360?days in air resulted in formation of a thin, adherent Al₂O₃ surface layer and a narrow Cr₇C₃ sublayer, accompanied by evaporation of carbon from the Cr₂AlC. Preferential oxidation of Al on the surface suppressed oxidation of the less mobile Cr in Cr₂AlC. In the Al₂O₃ layer, (0.7–8.3)?at.% Cr was incorporated. In the Cr₇C₃ sublayer, Al was either absent or incorporated. When Cr₂AlC oxidized at 850 and 1,000?°C for 30–360?days, metastable θ-Al₂O₃ blades formed on the α-Al₂O₃ layer. However, such blades were scarcely visible when the oxidation was carried out above 1,100?°C, because of the fast θ?→?α-transition. Moreover, the θ-Al₂O₃ were not noticeable during oxidation at 700?°C for 30–360?days, due to a small extent of oxidation.     

High-Temperature-Oxidation Behavior of Iron–Aluminide Diffusion Coatings

Aluminide diffusion coatings were oxidized in air under atmospheric pressure under isothermal and cyclic conditions. The high-temperature efficiency of the pack-aluminized alloys was tested by comparing their oxidation behavior in the temperature range 800–1080°C. The k _p values deduced from the parabolic plots of weight-gain curves showed that α-Al₂O₃ composed the major phase of the oxide scale on samples oxidized at T > 1000°C. For lower temperatures, transient-alumina phases were observed. The aluminide materials also exhibited excellent resistance to cyclic oxidation at 1000°C. The second aim of this study was to dope the aluminide compounds obtained by a pack-cementation process with yttria, which was introduced by metal-organic chemical-vapor deposition (MOCVD). The beneficial effect of the reactive-element-oxide coating is strongly dependent on its mode of introduction, since the oxidation resistance is drastically increased when the Y₂O₃ coating was applied prior to the aluminization process. When applied after the aluminization, the reactive element gave negative effects on the high-temperature oxidation behavior of the iron aluminides. The oxide morphologies, X-ray diffraction patterns and two-stage experiments helped to understand the oxide-scale-growth mechanisms.     

Thermal Stability and Oxidation Resistance of Pt–10 Al–4Cr Alloy at Super-High Temperatures

The isothermal-oxidation behavior of refractory superalloy Pt–10Al–4Cr (in at.%) was investigated up to a period of 312 hr in air from 1200 to 1400°C. A comparison of the oxidation behavior of this alloy with a conventional Ni-base superalloy (Inconel 713C) shows an order of magnitude higher oxidation resistance. This experimental alloy oxidizes by forming Al₂O₃ and Cr₂O₃ (and perhaps trace amounts of PtO) with Al₂O₃ as the oxide layer in contact with air. Optical and scanning-electron microscopy (SEM) were used to study the microstructure, morphology, and composition of the scale formed after oxidation. The thermal stability of the alloy after extended periods at 1200, 1300, and 1400°C was studied using transmission-electron microscopy (TEM).     

The influence of platinum on the maintenance of α-Al2O3 as a protective scale

The influence of externally located platinum on the isothermal stability of -Al₂O₃ scales formed at high temperatures has been examined. It has been observed that a nickel-base alloy forms an external scale of -Al₂O₃ during oxidation at 1200°C, but this scale breaks down isothermally, enabling a faster-growing Cr₂O₃-rich scale to develop. However, in the presence of platinum metal alongside the specimen in the furnace hot zone, the breakdown of the -Al₂O₃ scale is postponed for a substantial period of time. It appears that platinum, as the volatile species PtO₂, is incorporated into the growing -Al₂O₃ scale where it either influences the stress relief mechanism at temperature or reduces oxidation growth stress generation and thus significantly enhances the isothermal stability of the scale.     

TEM studies of cross sections of oxidized Fe-25Cr-6Al-La alloy

The oxidation behavior of the alloy Fe–25%Cr–6%Al-RE (rich in lanthanum) was investigated by means of TEM analysis. The results show that after 2 hr oxidation of the alloy, in pure oxygen at 1200° C, La precipitated in the oxide scale at the top of -Al₂O₃ grains and at the grain-boundary regions in the form of tiny particles of hexagonal La₂O₃. These tiny particles prevented aluminum from diffusing toward the surface and suppressed lateral growth of the oxide scale. The rare-earth constituents accelerated the internal oxidation of the alloy during thermal cycling between 1200° C and room temperature. They appeared as particles of aluminum oxide and lanthanum oxide. Particles of cubic La₂O₃ precipitated in the alloy matrix near the oxide scale-metal interface in a direction parallel to grain boundaries.     

The Oxidation Behavior of Y2O3-Dispersed β-NiAl

Y₂O₃-dispersed NiAl was produced by a powder-metallurgy process. By adding Y as an oxide dispersion (OD), problems with NiY_x formation and internal oxidation were avoided. Short-term isothermal and cyclic-oxidation performance at 1200°–1500° C was compared to cast NiAl alloys with and without Zr. Results indicate that the Y₂O₃ addition was beneficial to scale adhesion and significantly modified the α-Al₂O₃ scale microstructure, similar to a Zr alloy addition. However, at 1400 and 1500° C, neither the Y₂O₃ or Zr additions changed the scale-growth rate, eliminated the formation of voids at the metal-scale interface or prevented scale spallation. These similarities in performance suggest that similar mechanisms occur when the reactive element is added as either an OD or an alloy addition.     

Effect of Cr,Co, and Ti additions on the high-temperature oxidation behavior of Ni3Al

The oxidation behavior of Ni₃Al+2.90 wt.% Cr, Ni₃Al+3.35 wt% Co, and Ni₃Al+2.99 wt.% Ti alloys was studied in 1 atm of air at 1000, 1100, and 1200°C. Isothermal tests revealed parabolic kinetics for all three alloys at all temperatures. Cyclic oxidation for 28 two-hour cycles produced little spallation at 1000°C, but caused partial spallation at 1100°C. Especially, at 1200°C severe spallation in all three alloys was observed. Although additions of Cr, Co, or Ti to Ni₃Al alloys slightly increased the isothermal-oxidation resistance, the additions tended to decrease the cyclic-oxidation resistance. The major difference in the oxidation of the three alloys compared with the oxidation of pure Ni₃Al alloys was the existence of small -Al₂O₃ particles in the middle of the -Al₂O₃ scale and the formation of irregularly shaped Kirkendall voids at the alloy-scale interface.     

Corrosion of Cr2AlC in Ar/1%SO2 Gas Between 900 and 1200?��C

Cr₂AlC compounds were synthesized by a powder metallurgical route and corrosion tested at 900, 1000, 1100 and 1200 °C for up to 150 h under an Ar/1% SO₂ gas atmosphere. The compounds were resistant to corrosion because a thin ??-Al₂O₃ barrier layer quickly formed on the surface which suppressed sulfidation. Virtually no sulfur was detected inside the scale except during the initial corrosion stage. The superior corrosion resistance of Cr₂AlC originated from the high affinity of Al for oxygen to form the thermodynamically stable Al₂O₃. Unlike Al, Cr was not active because Cr was strongly bound to carbon as Cr₂C layers in Cr₂AlC. The small amount of Cr₂O₃ that had formed was dissolved in the Al₂O₃ layer. The corrosion of Cr₂AlC resulted in the formation of an ??-Al₂O₃ layer and an underlying Cr₇C₃ layer.     

Cyclic oxidation behavior of Ni3Al-7.8% Cr-1.3% Zr-0.8% Mo-0.025% B between 900 and 1100°C

A Ni₃Al-based alloy, the composition of which was Ni-16.0% Al-7.8% Cr-1.3% Zr-0.8% Mo-0.025%B, was cyclically oxidized in the temperature range of 900 to 1100°C in air for up to 500 hr. The alloy displayed good cyclic oxidation resistance up to 1000°C, with little scale spallation. It, however, lost cyclic oxidation resistance during oxidation at 1100°C after about 200 hr, displaying large weight losses due to serious scale spallation. NiO, α-Al₂O₃, NiAl₂O₄ and ZrO₂ were formed. The oxide scales consisted primarily of an outer Ni-rich layer which was prone to spallation, and (Al, Cr, Zr, Mo, Ni)-containing internal oxides which were adherent due mainly to the formation of (Al₂O₃, ZrO₂)-containing oxides that keyed the oxide scale to the matrix alloy.