Hot corrosion behavior of MCrAlY coatings on IN738LC

The hot corrosion behavior of CoNiCrAlY coatings deposited on IN738LC super alloy using low pressure plasma spray (LPPS) was investigated using samples immersed in a solution of Na₂SO₄-10 wt.% NaCl and dried as to be covered with a 2.5 mg/cm² costing. Specimens were heat-treated in furnace at 850 °C and after 24 h in the furnace were accurately weighed. Microstructural characterizations were carried out by scanning electron microscopy (SEM) equipped with energy dispersive spectroscopy (EDS) indicated interactions within microstructure of the coating with clearly diminished thickness of MCrAlY coating. Phase transformation and β-NiAl phase depletion in the MCrAlY coatings were shown to be directly related to the thermal cycles experienced by the samples and revealed outward diffusion of Al in the coating and the inward migration of Ni toward the coating causing β → γ′ phase transformation as the main cause of instability of the β-NiAl.     

TiAl合金表面激光重熔MCrAlY涂层热腐蚀性能

采用等离子喷涂技术在TiAl合金表面制备了MCrAlY涂层,并用激光重熔工艺对涂层进行处理,研究了TiAl合金、等离子喷涂MCrAlY涂层及激光重熔MCrAlY涂层850℃下75%Na₂SO₄+25%NaCl(质量分数)混合盐浸泡热腐蚀性能,分析了不同试样的热腐蚀破坏机理,并讨论了激光重熔处理对涂层热腐蚀性能的影响.结果表明,等离子喷涂MCrAlY涂层能显著提高TiAl合金的耐热腐蚀性能,经过激光重熔后可进一步提高其耐热腐蚀性能.MCrAlY涂层在高温熔盐中的热腐蚀发生的是表面氧化反应和内部硫化反应,主要生成Al₂O₃,Cr₂O₃,NiO,NiCr₂O₄,Ni₃S₂及CrS等腐蚀产物.     

The yttrium effect on the corrosion resistance of CO2-laser processed MCrAlY coatings

To improve the corrosion resistance and to study the effect of yttrium in the behavior of coatings produced by thermal spraying MCrAlY (M=Ni, Co) powders, CO₂ laser processing was conducted. Three methods were used: (1) a combination of gas flame and plasma spraying in air followed by laser glazing in argon, (2) low-pressure plasma spraying (LPPS) and laser glazing in argon, and (3) LPPS and laser-gas (O₂) alloying. Laser glazing in argon of the MCrAlY coatings sprayed in air promoted formation of weakly adherent agglomerates of Al–Y oxides and an alumina-chromia solid solution. Glazing in argon atmosphere of LPPS CoNiCrAlY and NiCrAlY coatings caused the formation of nickel aluminides besides the formation of Y–Al compounds. Gas (O₂)-alloying of these coatings produces continuous and adherent (yttrium-containing) alumina and chromia layers. The effects of yttrium on the characteristics of the oxides formed in the coatings during laser glazing, laser-gas alloying, and high-temperature oxidation is discussed. This work also investigated the oxidation resistance of the laser-processed MCrAlY coatings in air and in the presence of 85 mol/o V₂O₅–Na₂SO₄ fused salt at 900°C.     

Thermal expansion of Tribomet MCrAlY coatings

The thermal expansion behavior of seven Tribomet™ MCrAlY coatings was determined, using the PST Sapphire Dilatometer. Expansion equations were found vs. temperature and also vs. chemical composition. TM 301, NiCrAlY, has the lowest expansion of the group.     

Electrophoretic deposition of MCrAlY overlay-type coatings

A new process, which is a combination of electrophoretic deposition and pack cementation, was used to obtain MCrAlY overlay-type coatings. Using the electrophoretic-deposition process, rare-earth element is added to the deposits by using a special additive which contains yittrium, and excellent high-temperature corrosion resistance was observed after pack cementation.     

Drag reduction by corrosion inhibitors – A neglected option for mitigation of flow induced localized corrosion

Drag reduction, i.e. the influence of additives in the ppm‐range on the reduction of skin friction caused by turbulent flowing liquids, results from interaction of macromolecules and higher molecular micellar aggregates of amphipathic molecules with near‐wall turbulence elements. Drag reducing properties exhibited by corrosion inhibitors above critical concentrations decide on the level of critical wall shear stresses for initiation of flow induced localized corrosion (FILC). The relevance of drag reduction on FILC inhibition is explained with the newly developed probabilistic model of FILC initiation. The impinging jet method is recommended to quantify the effect of inhibitors on critical wall shear stresses by corrosion experiments and on drag reduction by electrochemically controlled mass transport measurements. Experimental evidence is given for FILC inhibition in CO₂ and H₂S corrosion systems. Drag reduction by corrosion inhibitors includes the interaction of shear‐induced molecular aggregate structures in near‐wall turbulences with adsorbates on the solid surface.     

Modelling of reinforcement corrosion – geometrical effects on macrocell corrosion

Reinforcement corrosion is still the most frequent reason for damage of concrete structures. It can be caused by carbonation or the ingress of chlorides. In cases of localized contaminations with chlorides, macrocells with very high corrosion rates can be established. Thereby the resulting macrocell current is dependent on many different boundary conditions like driving voltage, concrete resistivity and the geometrical arrangement of anode and cathode. In order to investigate macrocell corrosion, the herein presented research work was carried out by laboratory experiments and additionally by numerical analyses. First the numerical simulations were calibrated by laboratory measurements and thereafter, a numerical parameter study was carried out to increase the available database and identify the impact of changes in single parameters. As the focus is on geometrical effects, all laboratory specimens and numerical models were designed to represent practical conditions with diverse geometrical arrangements, e.g., slabs or beams with localized depassivations. In addition, parameters like concrete resistivity, driving voltage and cathode to anode surface area ratios have been varied. Thereafter, all results were used to derive cell factors for a simple macrocell current estimation. The present status of the project will be presented and discussed.     

Electrochemical investigations of organic,corrosion protective barrier coatings – limiting factors of small signal perturbation techniques

After a short introduction into the application of organic barrier coatings for corrosion protection the expectable parameters of the tested materials are discussed and the principle limitations are shown. Electrochemical impedance spectroscopy (EIS) is an already well known and also widely used technique, here only a very fundamental approach will be given. Relaxation voltammetry (RV) is a new electrochemical technology in the time domain. RV allows a two‐step data interpretation: first a very direct and easy accessible extraction of the coating resistance and coating capacity from the raw data. Second, a much more detailed interpretation of electrochemical processes in the coating in terms of dielectric relaxation, diffusion and charge transfer is presented and discussed in this paper.     

KCl‐induced corrosion of Ni‐based alloys containing 35–45 wt% Cr

Ni–(35–45)Cr–4Nb alloys containing different fractions of α‐Cr were exposed to potassium chloride (KCl)‐induced corrosion. The corrosion exposures were carried out for 168 hr at 600°C in a 15% (vol/vol) H₂O (g) + 5% (vol/vol) O₂ (g) + N₂ (g; balance) atmosphere using KCl‐free (reference) and predeposited KCl samples. To mimic the KCl deposition in real boilers, 24 hr exposures where KCl vapor condensed continuously onto samples were also performed. The corrosion attack of the studied materials increased significantly when KCl was present compared to the KCl‐free samples. For the KCl exposures, the corrosion attack drastically increased when a significant α‐Cr fraction was present. α‐Cr was either selectively attacked or dissolved through solid‐state diffusion and a layered build‐up of the outer external scale of K₂CrO₄ and chromia could be observed. For the in situ condensed KCl exposure, severe corrosion was observed already within the 24 hr exposure, indicating a higher corrosion rate compared with when KCl was predeposited.     

Modelling of reinforcement corrosion – Influence of concrete technology on corrosion development

Reinforcement corrosion is influenced by different parameters like resistivity of concrete, setting conditions and also by concrete technology. Moreover the presence of cathodic areas and the possibility of unhampered cathodic reaction influences the reinforcement corrosion. In this paper the development of corrosion without large cathodic areas, called self‐corrosion, considering different concrete parameters, is studied.     

Use of plasma spray technology for deposition of high temperature oxidation/corrosion resistant coatings – a review

High temperature oxidation is one of the main failure modes of the hot‐section components in gas turbines, boilers, waste incinerations, diesel engines, coal gasification plants, chemical plants and other energy generation systems. In such applications the use of Fe‐, Ni‐ and Co‐based alloys, especially of superalloys is well known. The superior mechanical strength and good corrosion resistance of the superalloys at high temperature make them favorites for such applications. However, the presence of combustion gases constitutes an extreme environment and hot corrosion is inevitable when superalloys are used at high temperatures for long durations of time. Therefore these alloys need to be protected against this type of oxidation. Several countermeasures have been suggested in the literature to combat the same. One such countermeasure against hot corrosion and oxidation constitutes the deposition of protective coatings on these alloys. Among the various techniques used for deposition of coatings, plasma spraying is a versatile technology that has been successful as a reliable cost‐effective solution for many industrial problems. It allows the spraying of a wide range of high performance materials from superalloys and refractory intermetallic compounds to ceramics with continuously increasing commercial applications. Furthermore it does not cause deterioration of the substrate alloys, and relatively thick coatings can be formed with high deposition rates. In this paper the technique of plasma spraying has been detailed and the role of plasma sprayed coatings to arrest high temperature oxidation has been discussed with the help of a comprehensive literature survey. The main focus of this investigation is the studies related to plasma sprayed NiCrAlY, Ni‐Cr, Nickel aluminide and Co‐based coatings.     

Damage process due to corrosion of Reinforcement bars – Current and future activities –

Against the background of huge costs for maintenance and repair it would be helpful to have a tool to assess the remaining life time of concrete structures. Deterioration is often caused by reinforcement corrosion and research projects have been carried out to develop models for the time‐dependent progress of the degradation. Although these projects have resulted in several steps forward, further work is still needed. This paper presents two actual research activities which deal with modeling of reinforcement corrosion: the first one is the RILEM Technical Committee MAI, the second is a German joint research project.     

Synthesis and oxidation behavior of nanocrystalline MCrAlY bond coatings

Thermal barrier coating systems protect turbine blades against high-temperature corrosion and oxidation. They consist of a metal bond coat (MCrAlY, M = Ni, Co) and a ceramic top layer (ZrO₂/Y₂O₃). In this work, the oxidation behavior of conventional and nanostructured high-velocity oxyfuel (HVOF) NiCrAlY coatings has been compared. Commercially available NiCrAlY powder was mechanically cryomilled and HVOF sprayed on a nickel alloy foil to form a nanocrystalline coating. Freestanding bodies of conventional and nanostructured HVOF NiCrAlY coatings were oxidized at 1000 °C for different time periods to form the thermally grown oxide layer. The experiments show an improvement in oxidation resistance in the nanostructured coating when compared with that of the conventional one. The observed behavior is a result of the formation of a continuous Al₂O₃ layer on the surface of the nanostructured HVOF NiCrAlY coating. This layer protects the coating from further oxidation and avoids the formation of mixed oxide protrusions present in the conventional coating. The original version of this article was published as part of the ASM Proceedings, Thermal Spray 2003: Advancing the Science and Applying the Technology, International Thermal Spray Conference (Orlando, FL), May 5–8 2003, Basil R. Marple and Christian Moreau, Ed., ASM International, 2003.     

Characterization of the corrosion products of electrodeposited Zn, Zn–Co and Zn–Mn alloys coatings

The morphology, composition, phase composition and corrosion products of coatings of pure Zn (obtained from two types of electrolytic bath: an acidic bath (Zn_acid) and a cyanide-free alkaline bath (Zn_alkaline)) and of Zn–Mn and Zn–Co alloys on steel substrates were studied. To achieve this, diverse techniques were used, including polarization curves, atomic force microscopy (AFM), scanning electron microscopy (SEM), glow discharge spectroscopy (GDS), X-ray diffraction (XRD), and the salt spray test. In the salt spray test, the exposure time required for the coatings to exhibit red corrosion (associated with the oxidation of steel) decreased in the following order: Zn–Mn_(432h) > Zn–Co_(429h) > Zn_{alkaline(298h)} > Zn_acid(216h). The shorter exposure times required for corrosion of the pure Zn coatings are related to the coating composition and the crystallographic structure. Analysis of the corrosion products disclosed that Zn₅(OH)₈Cl₂·H₂O was a corrosion product of all of the coatings tested. However, the formation of oxides of manganese (MnO, Mn_0.98O₂, Mn₅O₈) in the Zn–Mn coating, and the formation of the hydroxide Zn₂Co₃(OH)₁₀·2H₂O in the Zn–Co coating, produced more compact and stable passive layers, with lower dissolution rates.     

Modelling of reinforcement corrosion – Corrosion with extensive cathodes

Reinforcement corrosion is the most common reason for the premature deterioration of a concrete structure. In case of a partial depassivation of the reinforcement macrocells are formed with considerable metal removal rates. Thus an assessment of the macrocell current becomes of great concern. To find out, whether this can be achieved by numerical calculations, specimens have been fabricated and simulated by the use of a boundary element program. In this paper the results of the calculations are presented and compared to electrochemical measurements on the real specimens.     

Prevention of metal dusting on Ni-based alloys by MCrAlY coatings

The flame tubes from the domestic heating devices made of different Ni-based alloys (alloy 601/NiCr23Fe and even alloy 602/NiCr25FeAlY) showed after a short operation time severe attack by metal dusting. This phenomenon occurred only during combustion of the fuel oil with a new chemical composition. The german market offers such fuel oils with a reduced sulphur content due to more severe environment regulations. Sulphur is able to stabilize the cementite suppressing or retarding the appearance of metal dusting. Metallographical studies revealed that under this operation conditions the oxide scale on the Ni-based alloy forms only partially.In order to prevent the appearance of metal dusting, the flame tubes were coated by a high performance layer (MCrAlY-alloy) which shows a good stability under these corrosive conditions. Uncoated and MCrAlY-coated samples made of alloy 601 and alloy 602 were used for metal-dusting experiments. The specimens were tested using a computer-controlled special equipment which was developed and built in order to simulate the parameters in a flame tube of an oil heating device.Metallographical investigations of the tested samples revealed that the oxide scale present on the uncoated based alloy was formed only partially, whereas in the case of the MCrAlY coatings the oxide scale has an uniform distribution and a good stability due to the presence of the β-NiAl phase which is considered the Al-reservoir for its formation.