Reinterpretation of Type II Hot Corrosion of Co-Base Alloys Incorporating Synergistic Fluxing

The components of gas-turbine engines operating in marine environments are highly susceptible to hot corrosion, which is typically classified as Type II (650–750 °C) and Type I (900–950 °C) hot-corrosion attack. Even though hot-corrosion has been widely investigated in the last 50 years, several critical questions remain unanswered and new ones have emerged based on recent observations that, in part, are associated with the increasing complexity of the alloy systems and the sulfate-deposit chemistries. The present work is focused on the Type II hot-corrosion mechanism for Co-base alloys. Observations for a CoCrAlY model alloy (isothermally exposed at 700 and 800 °C under different atmospheres, including: air and O₂ with 100 and 1000 ppm SO₂) suggest the rapid dissolution of Co (as Co-oxide) is not the controlling factor in the degradation mechanism, as was proposed by Luthra, since the γ-phase which is richer in Co, is not attacked as significantly as the Al-rich β-phase. To the contrary, it is suggested that Al (and Cr) is (are) the element(s) which is (are) removed first. A modified interpretation of the Type II hot-corrosion mechanism is proposed, which is based on the synergistic fluxing model developed by Hwang and Rapp.     

Compositional Factors Affecting Protective Alumina Formation Under Type II Hot Corrosion Conditions

The Type II (700 °C) hot corrosion resistance of Ni–36Al (at.%) base alloys with various additions of Pt, Co, and/or Cr was investigated. It was found that the addition of either 5 at.% Pt or 5 at.% Cr was highly beneficial, i.e., extended the protective incubation stage. This was shown, via a thorough examination of the scales formed on these alloys during 700 °C oxidation, to be due to an enhanced ability to rapidly form a protective, pure Al₂O₃ scale. Addition of either 5 at.% Cr or 5 at.% Co to a Ni–36Al–5Pt alloy was found to be highly detrimental. These latter results are explained by examining subsurface phase transformations that occur during exposure; extensive transient oxidation was also found to play a significant role in the presence of Co.     

The Effect of Microstructure on the Type II Hot Corrosion of Ni-Base MCrAlY Alloys

Alloys of compositions (in wt%) Ni–31.5Cr–11.5Al–0.6Y and Ni–20.9Co–19.2Cr–12.5Al–0.5Y–0.4Si–0.3Hf were prepared using three different processing routes and exposed to Type II (700 °C) hot corrosion conditions in order to evaluate the influence of microstructural scale on degradation resistance. The alloys were prepared in bulk form by drop casting (DC) and injection casting (IC), and as a coating by low-pressure plasma spraying (LPPS) on a René N5 superalloy substrate. The resulting microstructures became coarser in the order LPPS < IC < DC for the NiCoCrAlY, and IC < LPPS < DC for the NiCrAlY. The DC and LPPS NiCrAlY displayed very good resistance to Type II hot corrosion; however, rapid Type II attack was observed when the alloy was prepared by the IC process. The LPPS and IC NiCoCrAlY formed more protective scales than the DC NiCoCrAlY, i.e., Type II hot corrosion resistance increased with microstructural refinement. Pre-oxidation of a cast NiCoCrAlY alloy greatly reduced the amount of Type II attack for the exposure times studied. The localized attack of the pre-oxidized specimens was found to initiate at reactive-element-rich regions in the pre-formed scale.     

The Influence of Specimen Thickness on the High Temperature Corrosion Behavior of CMSX-4 during Thermal-Cycling Exposure

CMSX-4 is a single-crystalline Ni-base superalloy designed to be used at very high temperatures and high mechanical loadings. Its excellent corrosion resistance is due to external alumina-scale formation, which however can become less protective under thermal-cycling conditions. The metallic substrate in combination with its superficial oxide scale has to be considered as a composite suffering high stresses. Factors like different coefficients of thermal expansion between oxide and substrate during temperature changes or growing stresses affect the integrity of the oxide scale. This must also be strongly influenced by the thickness of the oxide scale and the substrate as well as the ability to relief such stresses, e.g., by creep deformation. In order to quantify these effects, thin-walled specimens of different thickness (t = 100−500 μm) were prepared. Discontinuous measurements of their mass changes were carried out under thermal-cycling conditions at a hot dwell temperature of 1100 °C up to 300 thermal cycles. Thin-walled specimens revealed a much lower oxide-spallation rate compared to thick-walled specimens, while thin-walled specimens might show a premature depletion of scale-forming elements. In order to determine which of these competetive factor is more detrimental in terms of a component’s lifetime, the degradation by internal precipitation was studied using scanning electron microscopy (SEM) in combination with energy-dispersive X-ray spectroscopy (EDS). Additionally, a recently developed statistical spallation model was applied to experimental data [D. Poquillon and D. Monceau, Oxidation of Metals, 59, 409–431 (2003)]. The model describes the overall mass change by oxide scale spallation during thermal cycling exposure and is a useful simulation tool for oxide scale spallation processes accounting for variations in the specimen geometry. The evolution of the net-mass change vs. the number of thermal cycles seems to be strongly dependent on the sample thickness.     

Permeation of hydrogen in Ni-based superalloy CMSX-4

Permeation of hydrogen in CMSX-4 superalloy single crystals was studied by the volumetric method in the temperature interval from 573 to 1173 K. The measurements were carried out with two purity grades of hydrogen and for various sample thicknesses to estimate the influence of surface effects upon the permeation rate. The effect of phase transformation in the γ′ particles upon permeation rate was detected.     

Inhibition of Hot Corrosion by MgSO4 and BaSO4 and its potential dependence

Electrochemical corrosion measurements have been performed with IN 100 in a (mole %) 90 Na₂SO₄? 10 K₂SO₄ melt with different additions of MgSO₄ and BaSO₄ at 1173 K in order to investigate the inhibition effect of these compounds and its potential dependence. Potentiostatically controlled measurements as well as free corrosion potential measurements with the determination of the polarization resistance have been performed. The inhibition effect of MgSO₄ is strongly potential dependent. At negative potentials, where oxygen ions are produced by electrochemical side reactions, MgO is precipitated at the surface of the metal and becomes incorporated into the scale. This kind of MgO-rich scale is resistant to basic fluxing because MgO is not dissolved in basic media. At positive potentials, where acid SO₃ is produced by discharge of SO₄-ions, MgSO₄ yields no or only very little inhibition. BaSO₄ additions alone do not yield inhibition effects. However, additions of BaSO₄ to melts containing MgSO₄ improve the inhibition effect of the latter. The mechanism of this synergistic effect is not completely understood.     

Corrosion Behaviour of Type 316L Stainless Steel in Hot Caustic Aqueous Environments

Metals and Materials International - The corrosion behaviour of type 316L stainless steel in aqueous 30–50&nbsp;wt%. NaOH at temperatures up to 90&nbsp;°C has been elucidated....     

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.     

Hot Salt Corrosion of titanium aluminides

There is considerable interest in the use of γ-TiAl within advanced gas turbines where they offer greater high temperature capability over conventional titanium at reduced weight. These factors would enable engines with greater thrust to weight ratio to be developed. Thus γ-TiAl offers the potential of replacing nickel based alloys within the high pressure compressor and potentially the fourth stage turbine. Service in both of these locations would require that the γ-TiAl be resistant, not only to oxidation, but hot salt corrosion. This paper presents a study of the hot salt corrosion resistance of γ-TiAl over the temperature range 500–700°C. At 700°C, laboratory tests have shown that corrosion rates in a salt ladened environment are some 20X that of equivalent oxidation for exposures out to 100 h. The morphology of attack is consistent with a corrosion mechanism involving the vapour phase transport of aluminium from within the alloy and formation of a non protective oxide scale. A model for the corrosion mechanisms is presented, involving intermediate chloride phases. The mechanism is believed to be self sustaining, requires little chloride present, and leads to the observed accelerated oxidation rates.     

Hot Corrosion of Metals and Alloys

When metals and alloys are used at high temperatures, especially in combustion processes, deposits often accumulate on the metal surfaces and affect the oxidation processes. This paper is concerned with deposit-induced accelerated corrosion, or hot corrosion, of metals and alloys. Initially, the characteristics of hot corrosion are identified for Na₂SO₄ deposits in terms of the factors that influence the reaction process. It is shown that hot corrosion consists of initiation or incubation and propagation stages. During the initiation or incubation stage, the deposit is shown to not have a significant effect on the corrosion processes, but it is causing conditions to develop whereby the propagation stage characteristics are determined with attendant large increases in the corrosion rates. Type I, high temperature hot corrosion and Type II, low temperature hot corrosion are then described in terms of historical mechanistic perspectives. The dependence of Type I and Type II hot corrosion on temperature and SO₃ partial pressure is discussed along with future work that is needed in order to more completely understand these hot corrosion processes along with the effects of some elements such as Cr, Al, Mo, Co and Pt.     

Corrosion Behavior of IN-800 Superalloy in Waste-Incineration Environments: Hot Corrosion by Molten Chlorides

The corrosion resistance of the IN-800superalloy in contact with a molten mixture of (52-48)mol.% PbCl₂-KCl, similar to that found inwaste-incineration plants, has been studied. Thecorrosion kinetics have been analyzed using continuous-currentelectrochemical techniques and electrochemical-impedancespectroscopy (EIS). Studies were performed to determinethe influence of temperature and of the presence of carbon in the salt on the corrosion rate.Scanning electron microscopy (SEM) and electron probemicroanalysis (EPMA) were used as additional techniquesto analyze the corrosion products in order to elucidate the corrosion mechanism.     

Laboratory Studies of Galvanic Corrosion – II. Three-metal Couples

Electrochemical and weight loss measurements have been used to study galvanic corrosion of three-metal couples extending earlier studies of the galvanic interaction of two dissimilar metals. Materials studied include Zn, Cd, Cu, Ni, the Al alloys 2024, 6061 and 7075, 4130 steel, stainless steel 304, Ti-6Al-4V, Inconel 718 and Haynes 188 in 3.5% NaCl at 21°C. Different electrical arrangements for galvanic current measurements using the zero resistance ammeters (ZRA) are discussed. With the use of two ZRA's the current flowing on each of three metals can be continuously monitored. Weight loss data are used to obtain additional information concerning accelerated corrosion or protection of the individual metals in galvanic couples. Such measurements can be used to evaluate the corrosion behavior of metal combinations such as encountered in a porous Cd coating on a steel fastener installed on an Al structure.     

Thermodynamic and kinetic simulations of high temperature brazing: microstructure evolution in CMSX-4 joints

In this study, thermodynamic and kinetic simulations with Thermo-Calc and DICTRA software were utilised to predict the microstructural evolution observed in brazing of high-strength nickel base single crystal superalloy, CMSX-4, with two commonly used filler metals (FMs), AWS BNi-2 (AMS 4777) and AWS BNi-9. DICTRA diffusion models of the Ni-B binary system were used to calculate base materials dissolution, the amount of centreline eutectic constituents and time required for complete isothermal solidification at various joint gaps. Thermo-Calc simulations using the CALPHAD technique predicted transformation temperatures and equilibrium phases of the joints based on the chemical compositions of the two FMs. Experimental brazing and characterisations of joint microstructure at various brazing temperatures, hold times and joint gaps were used to validate the simulation modelling results. Good correlation with both Thermo-Calc and DICTRA simulations and empirical data demonstrated the benefits of using this modelling approach for braze joint development and applications.     

Effect of Heat Treatment on Chemical Segregation in CMSX-4 Nickel-Base Superalloy

Superalloys display a strong tendency toward chemical segregation during solidification. Therefore, it is of great importance to develop appropriate techniques for the melting and casting of superalloys. Elements partitioning between the γ and γ′ phases in single crystal superalloys have been investigated by several authors using electron probe microanalysis (Hemmersmeier and Feller-Kniepmeier Mater Sci Eng A 248:87-97, 1998; Kearsey et al. Intermetallics 12:903-910, 2004; Kearsey et al. Superalloys 2004, pp 801-810, 2004; D’Souza et al. Mater Sci Eng A 490:258-265, 2008). We examined the effect of the particular stages of standard heat treatment (solution treatment and ageing) applied to CMSX-4 single crystal superalloy on chemical segregation that occurs between dendrites and interdendritic areas. Dendritic structures were observed using a scanning electron microscope. Analyses of the chemical composition were performed using energy dispersive x-ray spectroscopy. The obtained qualitative and quantitative results for the concentrations of elements enabled us to confirm the dendritic segregation in as-cast CMSX-4 superalloy. The concentrations of some refractory elements (tungsten, rhenium) were much greater in dendrites than in interdendritic areas. However, these differences in chemical composition gradually decreased during heat treatment. The results obtained in this study warrant further examination of the diffusion processes of elements during heat treatment of the investigated superalloy, and of the kinetics of diffusion.     

CMSX-4单晶高温合金TLP接头组织与性能

采用含Si的BNi-5非晶箔片作为中间层合金对CMSX-4镍基单晶合金棒在放电等离子体烧结炉中进行TLP连接,采用SEM观测了TLP接头在不组织形貌特征,借助于EDS分析了TLP接头界面处的物相组成及其对接头力学性能的影响。采用常温和高温拉伸试验验证了不同焊接工艺条件对TLP接头性能的影响。结果表明,在1 200 ℃/5 kN/20 min工艺参数下可得到满意的TLP接头,此时组织分布较为均匀,常温抗拉强度达到了母材的95%,760 ℃高温抗拉强度达到母材的99%。     

Hot Corrosion Studies of HVOF-Sprayed Coating on T-91 Boiler Tube Steel at Different Operating Temperatures

The aim of the present work is to investigate the usefulness of high velocity oxy fuel-sprayed 75% Cr₃C₂-25% (Ni-20Cr) coating to control hot corrosion of T-91 boiler tube steel at different operating temperatures viz 550, 700, and 850 °C. The deposited coatings on the substrates exhibit nearly uniform, adherent and dense microstructure with porosity less than 2%. Thermogravimetry technique is used to study the high temperature hot corrosion behavior of uncoated and coated samples. The corrosion products of the coating on the substrate are analyzed by using XRD, SEM, and FE-SEM/EDAX to reveal their microstructural and compositional features for the corrosion mechanisms. It is found that the coated specimens have shown minimum weight gain at all the operating temperatures when compared with uncoated T-91 samples. Hence, coating is effective in decreasing the corrosion rate in the given molten salt environment. Oxides and spinels of nickel-chromium may be the reason for successful resistance against hot corrosion.     

Corrosion Behavior of 12CrMoV Steel in Waste Incineration Environments: Hot Corrosion by Molten Chlorides

The corrosion resistance of a 12CrMoV alloy incontact with a molten mixture of (52-48)mol.%PbCl₂-KCl, similar to that found inwaste incineration plants, has been studied. Thecorrosion kinetics have been analyzed using continuous-currentelectrochemical techniques and electrochemical impedancespectroscopy (EIS). Studies were performed to determinethe influence that temperature and the presence of carbon in the salt have on the corrosion rate.Scanning electron microscopy (SEM) and electron-probemicroanalysis (EPMA) were used as additional analyticaltechniques to analyze the corrosion products in order to elucidate the corrosionmechanism.