High temperature corrosion behavior of Ni-based alloys

The high temperature corrosion behavior of N07263, N06600, and N06625 in LiCl-Li₂O molten salt was investigated at temperatures ranging from 650 to 850 °C in a glove box. The high temperature corrosion behavior was observed using measurements of the oxide morphology and thickness, the extent of internal corrosion, and the compositional changes in the scale and in the substrate. Corrosion tests were performed, and these demonstrated that the main corrosion products were Fe(Ni,Co)₃, FeNi₃, and LiCrO₂. The internal corrosion of N07263 was localized, while that of N06600 maintained intergranular corrosion throughout the test temperature range. N06625 exhibited uniform intergranular corrosion behaviors at low and high temperatures. N07263 exhibited superior corrosion resistance, as evidenced by its corrosion layer which was more continuous, dense, and adherent when compared with those of N06600 and N06625.     

The high-temperature internal oxidation and intergranular oxidation of nickel-chromium alloys

The development of internal oxides and intergranular oxides in dilute NiCr alloys, containing 1–5% Cr, in NiNiO packs and in 1 atm oxygen at 800–1100°C has been investigated. The internal oxide particles were relatively coarse and widely spaced and were Cr₂O₃, except for a narrow band adjacent to the surface where NiCr₂O₄ particles were also present. Several types of intergranular oxide were developed in the Ni/NiO packs, with preferential penetration being more extensive in the higher chromium-containing alloys at the lower temperatures. Discrete intergranular oxide particles were formed deep in the alloy beneath bands of Cr₂O₃ which developed over intersections of the alloy grain boundaries with the surface, or beneath continuous or discontinuous grain-boundary oxides near the surface, possibly due to the development of a relatively flat oxygen profile and a steep chromium gradient in the subjacent alloy. In the presence of a thickening NiO external scale, preferential intergranular oxidation was much less extensive than in the Ni/NiO packs as the rapid growth of the scale prevented development of Cr₂O₃-rich surface bands.     

Corrosion behavior of NiCrMo Alloy 625 in high temperature, hydrogenated water

The corrosion behavior of NiCrMo Alloy 625 (UNS N06625) has been characterized in a 10,000 h test conducted in hydrogenated water at 260 °C. The corrosion kinetics were observed to be parabolic, the parabolic rate constant being determined by chemical descaling to be 0.074 mg dm⁻² h^−1/2. Characterizations of the corrosion oxide layer via grazing incidence X-ray diffraction and X-ray photoelectron spectroscopy in combination with argon ion milling and target factor analysis, revealed the presence of two spinel oxide phases and significant amounts of recrystallized nickel. Based on the distribution of three oxidized alloying constituents (Ni, Cr, Fe) with respect to depth and oxidation state, it was concluded that: (a) corrosion occurs in a non-selective manner, but significant amounts of nickel(II) ions are released to the water, and (b) the spinel oxides exist as a chromite-rich inner layer (Ni_0.7Fe_0.3)(Cr_0.8Fe_0.2)₂O₄ underneath a coarser, ferrite-rich outer layer (Ni_0.9Fe_0.1)(Cr_0.1Fe_0.9)₂O₄. The trivalent cation distribution in each of these phases appears to represent a solvus in the immiscible NiCr₂O₄-NiFe₂O₄ binary.     

Oxidation behavior of the single crystal Ni-based superalloy at 900 °C in air and water vapor

The oxidation behavior of a single crystal Ni-based superalloy TMS-82+ was studied in cyclic air and water vapor (air plus 15% H₂O) at 900 °C for 200 h. Oxidation kinetics was evaluated by mass gain measurements and the oxide scale was analysed by XRD, SEM and EDS, including the quantitative elemental concentration profiles by EPMA. Water vapor accelerated the growth rate of the oxides of NiO, Cr₂O₃ and spinel of NiCr₂O₄ due to the incursion of H, resulting in a higher mass gain and a thicker oxide scale with larger oxide grains of (Ni,Co)O.     

Oxidation behavior and mechanism of porous nickel-based alloy between 850 and 1000 °C

The oxidation behavior and mechanism of a porous Ni–Cr–Al–Fe alloy in the temperature range from 850 to 1000 °C were investigated by optical microscopy, scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) analyses and X-ray photoelectron spectroscopy (XPS). The results show that the oxidation kinetics at 950 and 1000 °C of this porous alloy is pseudo-parabolic type. Complex layers composed of external Cr₂O₃/NiCr₂O₄ and internal α-Al₂O₃ are formed on the surface of the oxidized porous alloys. γ' phases favor the formation of NiO/Cr₂O₃/NiCr₂O₄ during the initial oxidation. Many fast diffusion paths contribute to the development of the oxide layers. The decrease of the open porosity and the permeability with exposure time extending and temperature increasing can be controlled within a certain range.     

Surface Chemistry of Oxide Scale on IN-738LC Superalloy: Effect of Long-Term Exposure in Air at 1173 K

The oxidation kinetics of IN-738LC at 1173 K in dry air up to 1500 hr followed parabolic law. Surface morphology and the oxide phases present in the scale were characterized by SEM, XRD, EDS, FIB, and XPS. FIB investigation exhibited a compact and adherent oxide layer. XRD analysis revealed the presence of NiO, NiAl₂O₄, NiCr₂O₄ spinel, and Al₂O₃ on the top scale surface formed at 1173 K in dry air. Extensive XPS analyses revealed the presence of Cr₂O₃, CrO₂, and CrO₃ on the top scale surface formed on IN-738LC after 10 hr of exposure. The presence of TiO₂, Al₂O₃, Cr₂O₃, NiO, and NiAl₂O₄ and NiCr₂O₄ spinels along with the oxides of Ta at the top surface of the scale was observed after 100 hr of oxidation. The TiO₂ content was high on the surface and the entire scale cross section was composed mostly of Cr₂O₃, NiO, TiO₂, and Al₂O₃ after 100 hr of exposure to dry air at 1173 K. The concentration of Al₂O₃ on the surface of the oxide scale was found to increase after 100 hr of exposure and remained constant thereafter. After 300 and 1500 hr of exposure, the surface oxide was mainly Al₂O₃ along with oxides of Ni, Ti, and Cr. The oxide scale cross section consisted mostly of Al₂O₃ along with other oxides such as Cr₂O₃, NiO, and TiO₂. The oxide-scale composition was found to vary significantly with the duration of exposure to dry air at 1173 K.     

Hot corrosion behavior of ni-base superalloys in a lithium molten salt

The electrolytic reduction of a spent oxide fuel involves the liberation of the oxygen in a molten LiCl electrolyte, which is a chemically aggressive environment that is too corrosive for typical structural materials. Accordingly, it is essential to choose the optimum material for the process equipments such as the electroreducer and the salt purification vessel in the pyrochemical process. In this study, the corrosion behaviors of superalloys N-1, N-2 and N-3 in a molten LiCl-Li₂O salt under an oxidizing atmosphere were investigated at 650 °C for 72 h to 216 h. Superalloy N-1 showed the highest corrosion resistance among the examined alloys. The corrosion products of superalloys N-1 and N-2 were NiO, Cr₂O₃, and NiCr₂O₄, while NiO, Cr₂O₃, LiAl₂Cr₃O₈ were identified as the corrosion products of superalloy N-3. For superalloy N-1, its outer corrosion layer was more continuous, dense and adherent compared to those of N-2 and N-3.     

Oxide phase development upon high temperature oxidation of γ‐NiCrAl alloys

The amount of each oxide phase developed upon thermal oxidation of a γ‐Ni‐27Cr‐9Al (at.%) alloy at 1353 K and 1443 K and a partial oxygen pressure of 20 kPa is determined with in‐situ high temperature X‐ray Diffractometry (XRD). The XRD results are compared with microstructural observations from Scanning Electron Microscope (SEM) backscattered electron images, and model calculations using a coupled thermodynamic‐kinetic oxidation model. It is shown that for short oxidation times, the oxide scale consists of an outer layer of NiO on top of an intermediate layer of Cr₂O₃ and an inner zone of isolated α‐Al₂O₃ precipitates in the alloy. The amounts of Cr₂O₃ and NiO in the oxide scale attain their maximum values when successively continuous Cr₂O₃ and α‐Al₂O₃ layers are formed. Then a transition from very fast to slow parabolic growth kinetics occurs. During the slow parabolic growth, the total amount of non‐protective oxide phases (i.e. all oxide phases excluding α‐Al₂O₃) in the oxide scale maintain at an approximately constant value. The formation of NiCr₂O₄ and subsequently NiAl₂O₄ happens as a result of solid‐state reactions between the oxide phases within the oxide scale.     

The cyclic oxidation behavior of the single crystal TMS‐82+ superalloy in humidified air

The cyclic oxidation behavior of a single crystal Ni‐based superalloy TMS‐82+ was studied at 800 and 900 °C for 200 h in water vapor (air plus 15% H₂O). Regardless of the exposure temperature, time‐dependence of the growth rate of the scale for the superalloy was fitted by a subparabolic relationship. The oxidation rate was enhanced with increase in exposure temperature, which was evidenced by a higher mass gain and thicker scale. The oxides on the specimen at 800 °C consisted of (Ni,Co)O, CrTaO₄, AlTaO₄, Cr₂O₃, and θ‐Al₂O₃, whereas for the specimen exposed at 900 °C, spinels of NiCr₂O₄ and (Ni,Co)Al₂O₄ as well as α‐Al₂O₃ were observed. An innermost dense α‐Al₂O₃ layer was responsible for a stable growth rate of the scale after the initial rapid oxidation.     

不同Cr含量的Ni-Cr合金熔覆层的高温氧化和热腐蚀特性

采用激光熔覆技术制备了Cr质量分数为10%、20%和40%的Ni-Cr合金熔覆层,研究了其在900 ℃下的高温氧化特性和600 ℃下Na₂SO₄+25% K₂SO₄混合盐中热腐蚀特性。结果表明,Cr含量对熔覆层的高温特性起着关键作用。提高Cr含量对提升熔覆层抗硫酸盐诱导的热腐蚀能力比提升抗循环高温氧化能力更有效。Cr40涂层抗高温氧化和热腐蚀性能最佳。Cr10的氧化产物以NiO为主,极易脱落,内部氧化严重。虽然Cr40表面可以形成单一的Cr₂O₃层,但热应力和生长应力引起的富Cr氧化物内部开裂,使Cr40的抗循环高温氧化能力仅略好于Cr20。面对热腐蚀时,Cr10表面呈现层状NiO和Ni₃S₂叠层分布的腐蚀产物,内部腐蚀区也生成了Ni的硫化物。Cr20表面Cr₂O₃层被破坏,内部腐蚀严重,生成了CrS。Cr40表面生成了致密的Cr₂O₃保护层,有效地防止了进一步腐蚀。     

Corrosion behavior of Hastelloy C-276 in supercritical water

The corrosion behavior of a nickel-based alloy Hastelloy C-276 exposed in supercritical water at 500–600 °C/25 MPa was investigated by means of gravimetry, scanning electron microscopy/energy dispersive X-ray spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. An oxide scale with dual-layer structure, mainly consisting of an outer NiO layer and an inner Cr₂O₃/NiCr₂O₄-mixed layer, developed on C-276 after 1000 h exposure. Higher temperature promoted oxidation, resulting in thicker oxide scale, larger weight gain and stronger tendency of oxide spallation. The oxide growth mechanism in SCW seems to be similar to that in high temperature water vapor, namely solid-state growth mechanism.     

Type II Hot Corrosion Screening Tests of a Cr<Subscript>2</Subscript>AlC MAX Phase Compound

Low-temperature hot corrosion tests were performed on bulk Cr₂AlC MAX phase compounds for the first time. This material is a known alumina-former with good oxidation and Type I high-temperature hot corrosion resistance. Unlike traditional (Ni,Co)CrAl alumina formers, it contains no Ni or Co that may react with Na₂SO₄ salt deposits needed to form corrosive mixed (Ni,Co)SO₄–Na₂SO₄ eutectic salts active in Type II hot corrosion. Cr₂AlC samples coated with 20K₂SO₄–80Na₂SO₄ salt were exposed to 300 ppm SO₂ at 700 °C for times up to 500 h. Weight change, recession, and cross-sectional microstructures identified some reactivity, but much reduced (<?1/10) compared to a Ni(Co) superalloy baseline material. Layered Al₂O₃/Cr₂O₃ scales were indicated, either separated by or intermixed with some retained salt. However, there was no conclusive indication of salt melting. Accelerated oxidation was proposed to explain the results, and coarse Cr₇C₃ impurities appeared to play a negative role. In contrast, the superalloy exhibited outer Ni(Co) oxide and inner Cr₂O₃ scales, with Cr–S layers at the interfaces. Massive spallation of the corrosion layers occurred repeatedly for the superalloy, but not at all for Cr₂AlC. This indicates some potential for Cr₂AlC as LTHC-resistant coatings for superalloys.     

Influence of Water Vapor on the Cyclic-Oxidation Behavior of a Low-Pressure Plasma-Sprayed NiCrAlY Coating

The oxidation of a low-pressure plasma-sprayed (LPPS) NiCrAlY coating on a nickel-base superalloy was studied at 1050 °C in flows of O₂, and mixture of O₂ and 5% H₂O under atmospheric pressure. Water vapor has an obvious effect on the cyclic oxidation of the NiCrAlY coating. There is more decrease in weight gain when exposure to O₂ is replaced by exposure to O₂ + 5% H₂O. The oxide formed on the LPPS NiCrAlY coating after cyclic oxidation in pure oxygen is composed mainly of Cr₂O₃, and a thin Al₂O₃-rich layer is formed at the interface between the Cr₂O₃-rich layer and the coating. The oxide formed on the LPPS NiCrAlY coating after cyclic oxidation in a mixture of O₂ + H₂O is composed of NiCr₂O₄, NiO and Cr₂O₃. The effect of water vapor on the oxidation of the NiCrAlY coating may be attributed to an increase in Ni and Cr cation transport, stress-corrosion cracking of Al₂O₃ and moisture-enhanced volatility of the Cr₂O₃ scale.     

Improvement of the Oxidation Resistance of the Single-Crystal Ni-Based TMS-82+ Superalloy by Ni–Al Coatings with/without the Diffusion Barrier

Oxidation behavior of the uncoated base, Ni–Al coated and Re–Cr-Ni plus Ni–Al coated single-crystal (SC) Ni-based TMS-82+ superalloy is studied under cyclic air at 900 °C for 200 h to assess the oxidation resistance. Regardless of the coating processing, Ni–Al coating is effective in improving the oxidation resistance due to the formation of a continuous α-Al₂O₃ layer in the scale. For the uncoated base superalloy, the mass-gain curves are fitted by a subparabolic relationship, and complex oxide products including predominately NiO, some CrTaO₄, α-Al₂O₃, Cr₂O₃, a minor of spinels of (Ni, Co)Al₂O₄, AlTaO₄ and θ-Al₂O₃ are detected. Time-dependence of the oxide growth rate for both coated superalloy with/without the diffusion barrier is explained by the parabolic relationship. The oxide scales consist predominately of α-Al₂O₃ and a minor of θ-Al₂O₃. The diffusion barrier of σ-phase plays a negligible effect on the oxidation resistance during the cyclic exposure environment. The amount of detrimental γ′-phase and topologically close-packed (TCP) phases in the interdiffusion zone in the coated superalloy with the diffusion barrier is greatly reduced compared with that without the diffusion barrier due to the distinct barrier effect limiting diffusion of elements between the bond-coat and the substrate.     

Hot Corrosion Behavior of HVOF Sprayed Coatings on ASTM SA213-T11 Steel

Cr₃C₂-NiCr, NiCr, WC-Co and Stellite-6 alloy coatings were sprayed on ASTM SA213-T11 steel using the HVOF process. Liquid petroleum gas was used as the fuel gas. Hot corrosion studies were conducted on the uncoated as well as HVOF sprayed specimens after exposure to molten salt at 900 °C under cyclic conditions. The thermo-gravimetric technique was used to establish the kinetics of corrosion. XRD, SEM/EDAX and EPMA techniques were used to analyze the corrosion products. All these overlay coatings showed a better resistance to hot corrosion as compared to that of uncoated steel. NiCr Coating was found to be most protective followed by the Cr₃C₂-NiCr coating. WC-Co coating was least effective to protect the substrate steel. It is concluded that the formation of Cr₂O_3, NiO, NiCr₂O₄, and CoO in the coatings may contribute to the development of a better hot-corrosion resistance. The uncoated steel suffered corrosion in the form of intense spalling and peeling of the scale, which may be due to the formation of unprotective Fe₂O₃ oxide scale.     

Kinetics and Microstructural Investigation of High-Temperature Oxidation of IN-738LC Super Alloy

The present study was carried out to investigate the kinetics and the surface chemistry of the oxide layers formed on the IN-738LC super alloy during high-temperature oxidation at 950 °C in air from 1 to 260 h. Oxidation kinetics were studied by mass gain measurement. The oxide layers were characterized by field emission scanning electron microscope, elemental distribution map, energy-dispersive spectroscopy as well as x-ray diffractometry (XRD). The oxidation kinetics followed the parabolic law. The XRD analysis revealed that the oxide scale contained mainly NiO, Ni (Cr, Al)₂O₄, Al₂O₃, TiO₂ and Cr₂O₃. The oxide structure, from the top surface down to the substrate, was clarified by elemental map distribution studies as Ni-Ti oxides, Cr-Ti oxides, Cr₂O₃ oxide band, Ni-Co-Cr-W oxide and finally a blocky Al₂O₃ region. The oxidation scales were composed of three distinct layers of the outer and mid layers enriched by TiO₂ and Cr₂O₃, NiCr₂O₄ oxide, respectively, and the innermost layer was composed of Al₂O₃ and matrix alloy. The depleted gamma prime layer was formed under the oxidation scales due to the impoverishment of Al and Ti which were induced by the formation of Al₂O₃ and TiO₂.     

Studies on the Surface Chemistry of Oxide Films Formed on IN-738LC Superalloy at Elevated Temperatures in Dry Air

The oxidation behavior of IN-738LC was studied to develop high-temperature materials for low cost and highly efficient turbine systems. The present study was undertaken to investigate the kinetics and the surface chemistry of the oxide films formed during isothermal oxidation of IN-738LC superalloy in the temperature range 1123–1223 K in dry air. The oxidation kinetics followed the parabolic law. The activation energy of oxidation was 264 kJ mol–1. The scaling process is controlled mainly by the diffusion of chromium ions through the intermediate chromia layer in the scale. The surface morphology and the oxide phases of the scale were characterized by SEM, XRD, and EDS studies. XRD analysis revealed the presence of NiO, NiAl₂O₄, NiCr₂O₄ spinel, Al₂O₃, and Cr₂O₃ on the top-scale surface. The scale surface and cross section were further characterized using X-ray photoelectron spectroscopy (XPS), which revealed the presence of NiO, Ni₂O₃, NiAl₂O₄, Al₂O₃, and TiO₂ on the top-oxide surface. The chromia layer was found to be underneath the top scale. The chromia layer also contains NiCr₂O₄ and NiAl₂O₄ spinels along with Al₂O₃. Application of XPS was found to be successful to understand the oxide-scale chemistry in terms of the oxide-growth mechanism of IN-738LC at elevated temperatures.     

Relation between impurities and oxide-scale growth mechanisms on Ni-34Cr and Ni-20Cr alloys. II. Influence of sulphur

The oxidation of presulphidized Ni-Cr alloys has been studied by taking into account the influence of the two distinct oxidation mechanisms described in part I of this article. Sulphur enters the Cr₂O₃ scale (in Ni-34Cr alloys) mainly as S^2– species, which at high temperatures increases the V_Cr content, and hence the oxidation kinetics. Sulphur is randomly distributed in the scale, except at the inner oxide-alloy interface, where intergranular microsulphides are analyzed in the oxide-scale zone. In the case of NiO, NiCr₂O₄, Cr₂O₃ oxide multilayers (in a Ni-20Cr alloy), sulphur in the S^2– state is distributed in the oxide layers or at Si-precipitate interfaces. Such a distribution leads to crack formation, especially during cooling.     

Corrosion behavior of Ni−Base alloys in a hot lithium molten salt under an oxidizing atmosphere

The electrolytic reduction of a spent oxide fuel involves the liberation of the oxygen in molten LiCl electrolyte, which is a chemically aggressive environment that is excessively corrosive for typical structural materials. Accordingly, it is essential to choose the optimum material for the processing equipment that handles the molten salt. In this study, the corrosion behaviors of Haynes 263, Haynes 75, Inconel 718 and Inconel X-750 in a molten LiCl?Li₂O salt under an oxidizing atmosphere were investigated at 650°C for 72 to 216 hrs. The Haynes 263 alloy showed the best corrosion resistance among the examined alloys. The corrosion products of Haynes 263 were Li(Ni,Co)O₂ and LiTiO₂; those of Haynes 75 were Cr₂O₃, NiFe₂O₄, LiNiO₂ and Li₂FiFe₂O₄; while Cr₂O₃, NiFe₂O₄ and CrNbO₄ were identified as the corrosion products of Inconel 718. Inconel X-750 produced Cr₂O₃, NiFe₂O₄ and (Cr, Nb, Ti)O₂ as its corrosion products. Haynes 263 showed a localized corrosion behavior while Haynes 75, Inconel 718 and Inconel X-750 showed a uniform corrosion behavior.     

STUDY ON HOT CORROSION RESISTANCE OF A NEW DIRECTIONAL SOLIDIFICATION Ni–BASED SUPERALLOY

研究了新型定向凝固镍基高温合金DZ68的抗热腐蚀性能, 并与K438合金进行了比较. 结果表明: 热处理态DZ68合金组织中几乎没有(γ+γ') 共晶, 碳化物尺寸小,其整体组织比较均匀; 在热腐蚀过程中发生比较均匀的腐蚀, 其外腐蚀层的腐蚀产物主要是(Ni, Co)Cr₂O₄, 内腐蚀层的腐蚀产物主要是Al₂O₃. 热处理态K438合金组织中存在较多的 (γ+γ'共晶和数量较多、尺寸较大的长条状碳化物, 组织均 匀性较差; 在热腐蚀过程中发生不均匀腐蚀, 其外腐蚀层的腐蚀产物主要是NiO, 内腐蚀层的腐蚀产物主要是CrS.两种合金中Ti元素的偏析有促进其它元素偏析的倾向, 使合金组织的均匀性恶化,热腐蚀均匀性变差. 在本实验条件下, DZ68合金的抗热腐蚀性能略好于K438合金.