High temperature alloy chloridation at 850°C

The resistance of eight alloys against chloridation was tested at 850°C in Ar/Cl₂ (2.5% Cl₂) for 15 min. Pre‐oxidation treatments were performed for 1 h and 8 h at 850°C in order to produce a thin, adherent and protective oxide scale able to improve the chloridation behaviour of the tested materials. The chloridised sample morphologies were compared to the morphologies observed on the non pre‐oxidised samples. The alloys containing a large amount of iron did not exhibit any chloridation resistance, even after pre‐oxidation, and were severely damaged. The nickel based alloys gave interesting results but were also attacked by chloride, probably by the “active oxidation” mechanism. The duration of the pre‐oxidation treatment plays an important role, since the 8 h pre‐oxidation appears more beneficial than the 1 h pre‐oxidation, to delay the chloridation, probably because of the best quality of the oxide layer grown during 8 h. For the nickel based materials, the effects of chloride appear less severe than for the iron‐based alloys, but are not stopped. The “active oxidation” mechanism is proposed to be responsible for the degradation of the tested materials.     

Development of Re‐based diffusion barrier coatings on nickel based superalloys

A diffusion barrier type coating with a duplex layer structure, an inner σ‐(Re, W, Cr, Ni) as a diffusion barrier and outer Ni‐aluminide as an Al reservoir, was formed on a Nickel based, single crystal, superalloy (TMS‐82 +) and on Hastelloy X. Oxidation properties of both the alloys with or without the diffusion barrier coating were investigated in air under thermal cycling between room temperature and 1423 K for up to 360 ks. The inner σ layer with a composition (at%) of (35–40) Re, (15–20) W, (15–25) Cr and (15–25) Ni was produced by electrodeposition of Ni‐70Re and Ni‐20W films from aqueous solutions followed by Cr‐pack cementation at temperatures between 1473 and 1573 K, and the outer Ni‐aluminides of β‐(Ni,Cr)Al + γ′‐(Ni,Cr)₃Al was formed by electrodeposition of a Ni film, followed by Al pack cementation. After the 360 ks oxidation it was found that the structure and composition of both σ layer and alloy substrate were retained with little change. Furthermore, there was little Al in the σ layer. It could be concluded that the Re‐based alloys such as σ (Re(W),Cr,Ni) are very promising candidates as a diffusion barrier between the outer Al‐reservoir layer and alloy substrate at temperature of 1423 K. It was found that the Re(W)‐Cr‐Ni acts as a diffusion barrier for both inward diffusion of Al and outward diffusion of alloying elements in the alloy substrate.     

Effect of creep deformation on oxidation behavior of nickel‐based alloy with Re‐based diffusion barrier coating

Oxidation and creep behaviors of a Ni‐Mo‐based alloy (Hastelloy‐X) with a diffusion barrier coating consisting of duplex, inner Re‐based alloy, and outer β‐NiAl layers were investigated at 1243 K in air with an external tensile stress of 22.5 MPa. For comparison the alloys, as‐received, heat treated, and with the Ni‐aluminide coating, were oxidized under creep deformation. Creep rapture time for the diffusion barrier‐coated alloy was longer than those for the bare alloy and with the β‐NiAl‐coated alloy. After creep deformation to a strain of 3.5% for 190 h, it was found that the Re‐based alloy layer has few cracks and flaws and the β‐NiAl layer has the similar structure and composition before and after the creep test. The external scale mainly consisted of θ‐Al₂O₃ at the early stage of creep, and with further oxidation the external scale became a duplex layer, inner, equi‐axed α‐Al₂O₃, and outer, plate‐like θ‐Al₂O₃, which exfoliated significantly. It was concluded that the Re‐based alloy layer acts effectively as a barrier against inward Al diffusion and outward diffusion of alloy elements under creep deformation.     

Long‐term exposure of austenitic steels and nickel‐based alloys in lignite‐biomass cofiring

The aim of this study was to assess the long‐term impact that the addition of biomass provokes on superheater materials exposed to fireside corrosion environments. Alloys covering a broad range of commercially available materials were investigated. Their corrosion kinetics under different corrosive deposits and atmospheres was evaluated, and their corrosion products analyzed to deepen understanding of the underlying corrosion mechanisms. Therefore, three nickel‐based alloys and three austenitic steels containing 20–24 wt.% Cr were tested at 650°C for 7,000 hr. The long‐term exposure shows new mechanistic aspects of Type II hot corrosion that were revealed by accelerated material depletion. The formation of Ni–NiS eutectic and the formation of a Cr depleted zone close to the substrate corrosion product interface are indicative of the breakaway occurrence. Differences in the corrosion behavior are related to the balance of Ni, Mo, Co, and Cr and can serve as the material selection argument. The evaluation concluded with the finding that alloys presenting Mo and Ni might be preferentially used in fireside corrosion in the presence of biomass, whereas the use of austenitic steels suffer less corrosion if no biomass is present in the corrosive atmosphere.     

Corrosion and self‐healing behaviour of AZ91D magnesium alloy in ethylene glycol/water solutions

Corrosion behaviour of magnesium alloy‐based engine parts in cooling system is an urgent fundamental issue in automotive field where magnesium alloys are increasingly used. In the present work, the corrosion behaviour of AZ91D magnesium alloys in various ethylene glycol/water solutions was studied by electrochemical measurements and immersion tests at room temperature. The surfaces of the samples after immersion tests were examined using scanning electron microscope (SEM) and X‐ray diffraction (XRD). The results showed that the corrosion rates of AZ91D magnesium alloys decreased with the increase of ethylene glycol concentration in ethylene glycol/water solutions and the corrosion process was dominated by pitting corrosion. A continuous protective film transferred from corrosion products was formed on the corroded surface after sufficient immersion duration in ethylene glycol/water solutions, which is able to heal the corrosion pits. The self‐healing behaviour inhibited the further corrosion of AZ91D magnesium alloy.     

Einfluss der Halbzeugform auf die Korrosionsbeständigkeit hochlegierter Ni‐Cr‐Mo‐Werkstoffe

Effect of semi‐finished products on the corrosion resistance of high‐alloyed Ni‐Cr‐Mo materials The corrosion resistance of different semi‐finished products of six superaustenitic steels and nickel based alloys in the condition of delivery was investigated in some typical standard corrosion tests. The resistance of sheets, plates, strips, seamless tubes and welded tubes to intercrystalline corrosion was tested according to ASTM G 28 methods A and B, as well the resistance to pitting corrosion according to ASTM G 48 method C. The nickel based alloys 625, C‐276 and alloy 59 are resistant to the FeCl₃‐test according to ASTM G 48 method C and therefore a differentiation of these types in regard to their localized corrosion resistance was achieved only in the more aggressive ‘Green‐Death’‐solution. The laboratory experiments confirmed that the corrosion resistance is identical for all semi‐finished products and that it shows only a slight dependence of the surface condition of the materials tested. Additionally, some typical industrial and practical applications of the six high performance materials are presented to demonstrate the excellent corrosion resistance in the manufactured condition.     

Comparative study on corrosion protection properties of electroless Ni‐P‐ZrO2 and Ni‐P coatings on AZ91D magnesium alloy

Electroless Ni‐P‐ZrO₂ and Ni‐P coatings on AZ91D magnesium alloy were prepared, and their corrosion protection properties were compared in this paper. The potentiodynamic curves and electrochemical impedance spectroscopy (EIS) of the coated magnesium alloy in 3.5% NaCl solution showed that the corrosion performance of Ni‐P‐ZrO₂ composite coating was superior to that of Ni‐P coating. The same conclusion was obtained with salt spray and immersion tests. The corrosion morphologies of two kinds of coatings with various immersion time intervals in 3.5% NaCl solution indicated that most corrosion products concentrated on the nodules boundaries of Ni‐P coating and blocked corrosion pit was the main corrosion form. For the Ni‐P‐ZrO₂ coating, tortuous nodules boundaries were not the weak sites of the coating and corrosion initiated from the nickel phosphor alloy around the nanometer powders. Open corrosion pits occurred on the composite coating surface, and the coating was corroded gradually. Thus, the Ni‐P‐ZrO₂ coating exhibited better corrosion protection property to magnesium alloy substrate than Ni‐P coating.     

Corrosion characteristics of the wrought Ni‐Cr‐Mo alloys

This paper concerns the wrought, nickel‐chromium‐molybdenum (Ni‐Cr‐Mo) alloys, a family of materials with a long history of use in the chemical process industries. Their attributes include resistance to the halogen acids and resistance to pitting, crevice attack, and stress corrosion cracking in hot, halide salt solutions. The purpose of this paper is to characterize the performance of the Ni‐Cr‐Mo alloys in several key chemicals, using iso‐corrosion diagrams. These indicate the expected corrosion rates over wide ranges of concentration and temperature. Furthermore, the differences between individual Ni‐Cr‐Mo alloys, and their behavior relative to the stainless steels are defined. The data indicate benefits of both a high chromium content and a copper addition, as used in Hastelloy® C‐2000® alloy.     

Effect of different aging processes on the corrosion behavior of new Al–Cu–Li–Zr–Sc alloys

The intergranular corrosion and exfoliation corrosion behaviors of Al–Cu–Li–Zr–Sc alloys under different aging effects, such as single‐stage aging, strain aging, and double‐stage aging, were studied. Among the three aging treatments, single‐stage aging resulted in the best resistance to corrosion, followed by double‐stage aging; strain aging resulted in the worst corrosion resistance. A 3.5% precooling strain could increase the dislocation density, which promoted the precipitation of corrosion‐prone T₁ phase and increased the corrosion driving force of the alloy. Double‐stage aging made the precipitated T₁ phases finer and more uniform and reduced the number of equilibrium phases at grain boundaries, thus improving the corrosion properties of the alloy. The corrosion susceptibility of the alloy was attributed to the T₁ phase and precipitate‐free zone (PFZ), and the underlying corrosion mechanism was revealed as preferential dissolution of the equilibrium phase at grain boundaries and its surrounding distortion zone, followed by expansion of the PFZ along the grain boundaries, resulting in the development of corrosion from the grain boundaries to the intragranular regions.     

Oxidation mechanisms of Cr‐containing steels and Ni‐base alloys at high‐temperatures –. Part I: The different role of alloy grain boundaries

It is essential for materials used at high‐temperatures in corrosive atmosphere to maintain their specific properties, such as good creep resistance, long fatigue life and sufficient high‐temperature corrosion resistance. Usually, the corrosion resistance results from the formation of a protective scale with very low porosity, good adherence, high mechanical and thermodynamic stability and slow growth rate. Standard engineering materials in power generation technology are low‐Cr steels. However, steels with higher Cr content, e.g., austenitic steels, or Ni‐base alloys are used for components applied to more severe service conditions, e.g., more aggressive atmospheres and higher temperatures. Three categories of alloys were investigated in this study. These materials were oxidised in laboratory air at temperatures of 550°C in the case of low‐alloy steels, 750°C in the case of an austenitic steel (TP347) and up to 1000°C in the case of the Ni‐base superalloys Inconel 625 Si and Inconel 718. Emphasis was put on the role of grain size on the internal and external oxidation processes. For this purpose various grain sizes were established by means of recrystallization heat treatment. In the case of low‐Cr steels, thermogravimetric measurements revealed a substantially higher mass gain for steels with smaller grain sizes. This observation was attributed to the role of alloy grain boundaries as short‐circuit diffusion paths for inward oxygen transport. For the austenitic steel, the situation is the other way round. The scale formed on specimens with smaller grain size consists mainly of Cr₂O₃ with some FeCr₂O₄ at localized sites, while for specimens with larger grain size a non‐protective Fe oxide scale is formed. This finding supports the idea that substrate grain boundaries accelerate the chromium supply to the oxide/alloy phase interface. Finally, in the Ni‐base superalloys deep intergranular oxidation attack was observed, taking place preferentially along random high‐angle grain boundaries.     

Electrochemical response of amorphous and devitrified Al‐Ni‐La‐X (X = Ag,Cu) alloys

The electrochemical response of melt‐spun Al‐Ni‐La alloys with partial substitution of Ni after different stages of devitrification was studied. The base alloy was found to have the best corrosion resistance. It was observed that primary crystallization caused minimal deterioration in the corrosion resistance of the base alloy as compared to its amorphous state. The substitute alloys had different corrosion resistance dependent on the substituting element with the Ag containing alloy having the least resistance. This could be attributed to the operation of local galvanic cells, enhanced by chemical heterogeneities in the alloys. Secondary crystallization caused a reduction in the corrosion resistance of all the alloys due to the creation of intermetallic phases that increased the galvanic activity.     

Corrosion of alloys and their diffusion aluminide coatings by KCl:K2SO4 deposits at 650 °C in air

P91 ferritic‐martensitic steel, 17Cr–13Ni and alloy 800 austenitic stainless steels and Inconel 617 alloy have been aluminised to form Fe₂Al₅, (Fe,Ni)Al and Ni₂Al₃ aluminide coatings. These alloys and their corresponding coatings were subjected to corrosion in air by 50:50 mol/mol K₂SO₄/KCl deposits at 650 °C for 300 h. With the exception of the Inconel 617 alloy, significant metal losses (>180 µm) were recorded. These losses were planar for P91 alloy but involved internal corrosion for the two austenitic steels. The (Fe,Ni)Al and NiAl coatings on the austenitic steels and the Inconel 617 alloy were significantly corroded via intergranular and internal chloridation–sulphidation–oxidation. In contrast, the Fe₂Al₅ coating on the P91 alloy coating was virtually unattacked. For the alloys, the relative extents of corrosion damage can be explained in terms of the stability and volatility of metal chlorides formed. For the coatings, STEM/EDS analyses enable clear linkages to be made between the presence and number of Cr‐rich particles on coating grain boundaries and the corrosion damage observed for the coatings.     

Nitridation in NH3‐H2O‐mixtures

Exposures were conducted of iron, nickel, ferritic 1‐18%Cr steels, austenitic 18%Cr‐9%Ni‐ and 20%Cr‐31%Ni‐steels and a 16%Cr‐Ni‐base alloy at 500°C in He‐30%H₂O and 70%H₂O‐30%NH₃, to compare the corrosion behaviour of these materials in water vapor as in conventional power plants with their behaviour in a NH₃‐H₂O mixture, i.e. under conditions of the “Kalina‐cycle”. After 50 h in He‐H₂O generally a dense oxide scale had grown on iron and on the steels, whereas the scale grown in NH₃‐H₂O was porous, due to initial formation of the γ′‐ and ε‐nitrides, which are converted to Fe₃O₄ later. The porous scale allows internal nitridation of the Cr‐steels, nitrogen is transferred into the metal phase and reacts to finely dispersed CrN‐precipitates. This process causes stresses in the material and formation of cracks. The higher the Cr‐content of the material, the worse is the damage of the materials surface. Least corrosion damage occurs for iron and the 1%CrMo‐steel, however, the inward penetration of nitridation is greatest, and after 5 years on the low Cr‐steel a layer of about 15 mm would be embrittled by internal nitridation, formation of γ′ and ε‐nitride layers and external oxidation. Nickel is strongly damaged by intermediate formation of instable Ni₃N, which causes internal stresses and cracking, but also pore formation by its decomposition. The surface region of the 15%Cr‐Ni‐base alloy is also destroyed by internal nitridation and extrusion of Ni‐particles, while for this material the inward penetration of nitridation is relatively slow due to the low solubility and diffusivity of N in Ni and Ni‐alloys.     

Microstructural investigation of PGM‐based alloy coatings for oxidation protection

It is well known that Pt addition significantly improves the resistance of aluminide coatings to high‐temperature oxidation and hot corrosion, which has led to the widespread application of Pt modified aluminide coatings on the superalloy components of advanced gas turbine engines. Other platinum group metals (PGMs) such as Ir and Ru attract researchers for high temperature applications. In this study, oxidation properties of Pt‐Ir and Pt‐Ru based alloy coatings were investigated. Pt, Ru, and Ir were electroplated on a directionally solidified Ni‐base superalloy DZ125. The cyclic oxidation test revealed that both Pt‐Ir and Pt‐Ru alloys exhibited good oxidation performance. The effect of substrate alloy and coating compositions on microstructural changes during cyclic oxidation tests were discussed.     

Oxide scale formation on Al containing Ni–Cr‐based high temperature alloys during application as flame tube material in recirculation oil burners

The flame tube is an important functional component of burners using the concept of the flame tube stabilised combustion. Under typical combustion conditions the material of the flame tube is exposed to high temperatures (≥900 °C) and to corrosion attack by the combustion gases. Furthermore as the burners are generally operated intermittently, the material suffers from extreme temperature and atmosphere changes. For flame tubes, a lifetime of approximately 8000 h is desired. Predominantly metallic high temperature materials are used. The scope of the present work was to test—under application conditions and for maximum material temperatures exceeding 900 °C—alternative high temperature alloys for use as tube material. The corrosion resistance of the austenitic Ni–Cr‐based alloys (601, 602 CA, 617 and 693) has been investigated in a burner rig at maximum material temperatures of 950 and 1000 °C and with exposure times from 50 to 3000 h. The chromium content of the alloys was between 20 and 30 wt% and that of aluminium between 1 and 3.4 wt%. Metallographic cross‐sections of samples of the alloys were analysed by electron microprobe yielding information about the microstructure and composition of the oxides in the surface zone and variations during exposure time. This study focuses on the observed specific effects of the alloying element aluminium on the development of the oxide scale and on the lifetime of the alloys. At the alloy surface after 500 h exposure time a chromium oxide scale had formed with aluminium oxides underneath predominantly along grain boundaries. For the alloys with the lower aluminium content, the aluminium oxides built up an open network but not a closed layer. For the alloy with the highest aluminium content (alloy 693) after 50 h two different characteristic microstructures at the surface were found. In one case, the grains at the surface were covered with chromium oxide on top and the remaining grain surface was completely enclosed by aluminium oxides. In the other case, the aluminium oxide formed a thin layer directly below the chromium oxide scale. After 500 h exposure time, a significantly thinner chromium oxide scale and massive internal chromium oxides were observed. Catastrophic corrosion, formation of internal oxides and aluminium nitrides started even after 500 h. It will be demonstrated that the early breakdown of alloy 693 is linked to the aluminium oxides which act as a barrier constricting the diffusion of chromium from the alloy matrix towards the surface. Under the conditions of extreme temperature changes given in the burner the aluminium oxide layer on its part did not provide corrosion protection.     

SVET study of the corrosion protection of electrodeposited Zn and Zn‐Co‐Fe alloy coated steels

The scanning vibrating electrode technique (SVET) was applied to study the corrosion resistance of partially coated (Zn and various Zn‐Co‐Fe alloys) and partially exposed steel samples in 10 mM NaCl solution. The sacrificial properties and the protection range decreases with increase in Co content in the alloy. For high Co content in the alloy, the coating becomes more noble to steel and loses its sacrificial protection. The barrier resistance of the coatings increases with the increase in Co content in the alloy coating. Zn‐Co‐Fe alloys with high Co content (i.e., 32 wt% Co and 1 wt% Fe) showed excellent barrier properties due to passivation after dezincification protecting the underlying steel. An intermediate region of compositions can be distinguished in which the coatings provide a good combination of sacrificial and barrier resistance properties and also a reasonable protection range.     

Effect of nitriding on the electrochemical behaviour of Ti‐Al‐Mn alloy

The effect of technological conditions of nitriding such as process time duration and chemical composition of saturating medium, on the corrosion behaviour of nitrided coatings in 14 M solution of sulphuric acid was analyzed. The investigations were done on the alloy Ti‐5,0 Al‐2,0 Mn. The nitriding was carried out in nitrogen both at atmospheric pressure and rarefied nitrogen pressure (1 Pa) at the temperature 850°C and time processing in the range from 5 to 20 h in nitrogen‐containing gas only, and in powder electrode graphite and nitrogen‐containing gas. It was shown that technological conditions of nitriding determine the protective properties of nitrided coatings. It was indicated that the optimal structure of the nitride layer for best corrosion protection is the thin nitride TiN_x with high surface quality and a gas‐saturated layer. Nitriding in graphite powder effects positively the protective properties of nitride coatings due to reducing the nitride‐forming process.     

Corrosion behaviour of the new gas turbine alloy 2100 GT in hot gases and combustion products

Not only excellent high temperature mechanical properties are needed to establish a new gas turbine alloy, but also a very good oxidation behaviour, together with good resistance to so‐called “hot corrosion”. This paper describes experimental studies on the corrosion behaviour in hot gases and combustion products of a new Ni‐Cr‐Ta alloy 2100 GT in comparison to the commercially established alloys 230, C‐263 and 617. Alloy 2100 GT is a newly developed cobalt, tungsten and molybdenum free Ni‐base superalloy of Krupp VDM. It contains as major alloying elements 25 wt.‐% chromium, 8 wt.‐% tantalum, 2.4–3 wt.‐% aluminium and 0.2–0.3 wt.‐% carbon. High temperature strength is achieved by the addition of tantalum, resulting in significantly increased solid solution strengthening, carbide hardening due to the formation of primary precipitated tantalum carbides, and γ′‐precipitation hardening by aluminium and tantalum. The isothermal oxidation tests showed that the parabolic rate constant of alloy 2100 GT is similar to that of alumina‐forming alloys. This is achieved by the remarkably high aluminium content for a wrought alloy. Additions of yttrium improve the spalling resistance under thermal cycling by the formation of very thin and tightly adherent oxide layers. No deleterious effect caused by the addition of tantalum could be found. In the cyclic oxidation tests performed at temperatures between 700°C and 1200°C alloy 2100 GT showed the lowest mass change of all the alloys investigated. Na₂SO₄ has been found to be a dominant component of alkali salt deposits on gas turbine components at elevated temperatures. Combustion gases contain SO₂ because of the impure nature of the fuel. To investigate the hot corrosion behaviour of alloy 2100 GT, tests were performed with salt deposits containing 0.1 mol Na₂SO₄ and a test gas comprising air and 0.1% SO₂. Test temperatures were 600°C, 700°C, 850°C and 950°C. Alloy 2100 GT exhibited the best performance at all test temperatures. It was the only alloy which did not suffer any fluxing of the oxide layer and only slight internal sulphidation was observed.     

Corrosion behavior of Fe(Ni)CrAIX alloys in an HCl−H2O−H2 gas mixture at 800°C

The high-temperature-corrosion behavior of a series of Fe(Ni)CrAlX-type alloys (where X=Zr and Hf, e.g.) has been studied in a gas mixture of 50% HCl-10% H₂O–H₂ at 800°C. The experimental results obtained indicated that Ni-base alloys had superior corrosion resistance to Fe-base alloys in this gas mixture. While the exposed Ni-base alloys showed weight gains due to the formation of oxides (e.g., Al₂O₃, Cr₂O₃) as well as CrCl₂, the Fe-base alloys exhibited substantial weight losses resulting from the formation and subsequent evaporation of FeCl₂. This study also demonstrated that Fe(Ni)Cr8AlX-type alloys, which contained high aluminum, had better chloridation resistance than Fe(Ni)25CrAlX-type alloys, which had high chromium. The improved performance of Fe(Ni)Cr8AlX-type alloys was due to the presence of a high level of aluminum which promoted formation of protective Al₂O₃. Although the presence of chromium in the alloys promoted the formation of Cr₂O₃, the high level of chromium adversely affected the chloridation resistance of Fe(Ni)25CrAlX-type alloys, due to the development of chloride (CrCl₂) at the interface of the oxide scale and alloy substrate.     

Corrosion behavior of under‐, peak‐, and over‐aged 6063 alloy: A comparative study

The mechanical property of age‐hardenable Al‐alloys is governed by the state of ageing, which determines the microstructure and consequently, their corrosion behavior which is a vital aspect for a number of applications. This article presents a comparative assessment of corrosion behavior of under‐, peak‐ and over‐aged Al‐Mg‐Si alloy. Corrosion characteristics have been determined via immersion tests in 0.1 M ortho‐phosphoric acid solution and intergranular corrosion (IGC) tests. Corroded surfaces are examined by field emission scanning electron micrographs‐energy dispersive spectroscopy and 3D optical profilometer. The obtained results reveal that the corrosion rate at a specific immersion time as well as the depth of IGC increases in the order for under‐, peak‐, and over‐aged states. Irrespective of the state of ageing, corrosion loss increases linearly but the rate of corrosion decreases rapidly with increasing immersion time. The dominant mode of corrosion in under‐aged alloy is identified as localized pitting, while peak‐aged is highly susceptible to IGC in contrast extensive pitting corrosion is observed for over‐aged alloy. The observed differences in corrosion behavior are explained considering characteristics of precipitates. Formation of β (Mg₂Si) in case of over‐aged alloy and presence of inclusions like AlFeMnSi particles are found to accelerate pitting corrosion.