Interdiffusion behavior of Al‐rich oxidation resistant coatings on ferritic–martensitic alloys

Interdiffusion of thin Al‐rich coatings synthesized by chemical vapor deposition (CVD) and pack cementation on 9Cr ferritic–martensitic alloys was investigated in the temperature range of 650–700 °C. The compositional changes after long‐term exposures in laboratory air and air + 10 vol% H₂O were examined experimentally. Interdiffusion was modeled by a modified coating oxidation and substrate interdiffusion model (COSIM) program. The modification enabled the program to directly input the concentration profiles of the as‐deposited coating determined by electron probe microanalysis (EPMA). Reasonable agreement was achieved between the simulated and experimental Al profiles after exposures. The model was also applied to predict coating lifetime at 650–700 °C based on a minimum Al content (C_b) required at the coating surface to re‐form protective oxide scale. In addition to a C_b value established from the failure of a thin CVD coating at 700 °C, values reported for slurry aluminide coatings were also included in lifetime predictions.     

The Effect of Water Vapor on the Oxidation Behavior of CVD Iron-Aluminide Coatings

The oxidation behavior of iron-aluminide coatings, Fe₃Al or (Fe,Ni)₃Al, produced by chemical-vapor deposition (CVD) was studied in the temperature range of 700–800°C in air + 10 vol.% H₂O. A typical ferritic steel, Fe–9Cr–1Mo, and an austenitic stainless steel, 304L, were coated. For both substrates, the as-deposited coating consisted of a thin (<5μm), Al-rich outer layer above a thicker (30–50 μm), lower-Al-content inner layer. In addition to coated and uncoated Fe–9Cr–1Mo and 304L, cast Fe–Al model alloys with similar Al contents (13–20 at.%) to the CVD coatings were included in the oxidation exposures for comparison. The specimens were cycled to 1000 1 hr cycles at 700°C and 500 1 hr cycles at 800°C, respectively. The CVD coating specimens showed excellent performance in the water-vapor environment at both temperatures, while the uncoated alloys were severely attacked. These results suggest that an aluminide coating can substantially improve resistance to water-vapor attack under these conditions.     

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.     

Protective behaviour of newly developed coatings against metal dusting

Metal dusting is a corrosion phenomenon whose mechanisms and effects depend on different parameters such as temperature, pressure, time, material, etc. and which still leads to unexpected failure cases in several high temperature industries. The present work deals with the development and testing of coating systems against metal dusting attack and the evaluation of their protective behaviour at different temperatures. The recently developed coatings are based on high amounts of strong oxide formers, like Si, Ti, Cr and Al, which are able to form protective oxide layers even under the highly reducing metal dusting atmospheres. The coatings were applied on ferritic and austenitic steel substrates by HVOF and by (co) diffusion of one or up to three elements via a pack cementation process. The process parameters of the diffusion coatings were optimized with respect to the different substrate materials and diffusing species. Isothermal tests at temperatures of 400°C, 620°C and 700°C under metal dusting atmospheres were carried out for up to 2022 h for coated and uncoated specimens. Discontinuous mass change measurements were performed in order to determine the kinetics of attack. After the corrosion tests metallographic cross sections of the specimens were investigated by optical and electron microscopy (SEM, EPMA). Especially the interdiffusion of substrate and coating and the formation of potentially protective oxide layers on top of the coatings were studied using elemental mapping and concentration profiles. The results obtained so far indicate that coatings have a high potential for significantly increasing the life‐time of components under metal dusting conditions. The different systems investigated are classified, evaluated, and discussed with respect to their protection potential and the responsible protection mechanisms.     

TG–mass spectrometry studies in coating design for supercritical steam turbines

Ferritic steels in steam turbines for the power industry operate without coatings in the temperature range of 590–600 °C. For higher operation temperatures the substrate has to be replaced or coated, otherwise the ferritic substrate at a temperature of 650 °C develops thick oxide scales that promote sudden turbine blade failure. The advantage of the use of coatings is that coated ferritic steels are much less expensive than austenitic stainless steels or nickel base superalloys. In order to go forward to coatings design, the Thermo‐Calc code was used as a base for the mass spectrometry (MS)‐data. Thermogravimetry (TG)–MS experiments were conducted in a closed steam loop in order to obtain information about the oxyhydroxides formation as reaction between coatings and steam. From those results the role of the different coating element could be established and optimized for the coating durability. An oxidation mechanism based on the TG–MS results is given.     

Ni–Al composite coatings: diffusion analysis and coating lifetime estimation

The interdiffusion of Ni matrix/Al particle composite coatings and nickel substrates was studied using electron probe microanalysis (EPMA) and a one-dimensional diffusion model. The initial coating microstructure was a two-phase mixture of γ(Ni) and γ′(Ni₃Al). The coating/substrate assemblies were aged at 800 to 1100°C for times up to 2000 h. It was found that aluminum losses to the substrate are significant at 1000°C and above. The experimental results for the diffusion of Al into the substrate were compared with model predictions based on a diffusion equation for a finite layer on an infinite substrate. Using combined experimental and model results, the effects of temperature and coating thickness were determined and a rationale was developed for coating lifetime prediction.     

Development of novel diffusion coatings for 9–12 % Cr ferritic‐martensitic steels

Eventhough 9–12% Cr steels are mechanically designed for power plant applications up to 650 °C, their effective use is limited by the corrosion resistance at this temperature. Therefore, the present paper addresses the development of diffusion coatings on 9% Cr ferritic‐martensitic steels. The difficulty of coating these materials with conventional diffusion processes arises from the temperature limit above which the conversion of the martensite is accelerated and the mechanical properties would be deteriorated. Aluminide coatings consisting of Fe₂Al₅ or FeAl phases were thus developed for deposition temperatures between 650 and 715 °C by the conventional pack cementation technique. As the addition of boron was expected to improve the oxidation properties of the coating, the influence of B on the aluminide coating was investigated. The precedent diffusion of Cr as an interdiffusion barrier before switching to the Al diffusion step was also investigated. As a further technique, the fluidised bed chemical vapour deposition (FBCVD) method allowed the development of Fe₂Al₅ coatings at 550 °C. Furthermore, Si or codiffusion Al‐Si coatings were developed at temperatures as low as 550 °C.     

NiCoCrAlY coatings with and without an Al2O3/Al interlayer on an orthorhombic Ti2AlNb-based alloy: Oxidation and interdiffusion behaviors

The mechanism of oxidation protection of NiCoCrAlY overlay coatings on the orthorhombic Ti₂AlNb-based alloy (O alloy) Ti–22Al–26Nb (at.%) is described. While the bare alloy exhibited poor oxidation resistance at 800 °C, adding NiCoCrAlY coatings significantly improved the oxidation resistance. However, serious interdiffusion between the coatings and the substrate resulted in rapid degradation of the coating system. Several reaction layers were formed at the coating/substrate interface by interdiffusion, and non-protective scales mainly of Cr₂O₃ and TiO₂ were formed due to the degradation of the coating. In order to solve this problem, an Al₂O₃/Al interlayer was sandwiched into the coating system as a diffusion barrier. The isothermal and cyclic oxidation protection of the multilayer coating system on the Ti–22Al–26Nb substrate was evaluated at 800 and 900 °C. The results indicated that the interdiffusion was much suppressed, and the duplex coating system demonstrated improved oxidation resistance on the Ti–22Al–26Nb substrate, with a thin and adherent protective α-Al₂O₃ scale forming on the surface.     

Oxidation behavior of arc-sprayed FeMnCrAl/Cr3C2-Ni9Al coatings deposited on low-carbon steel substrates

FeMnCr/Cr₃C₂ and FeMnCrAl/Cr₃C₂ coatings, using Ni9Al arc-sprayed coating as an interlayer on low-carbon steel substrates, were deposited by high velocity arc spraying (HVAS) on the cored wires. The high temperature oxidation behavior of the arc-sprayed FeMnCrAl/Cr₃C₂-Ni9Al and FeMnCr/Cr₃C₂ coatings on the low-carbon steel substrates was studied during isothermal exposures to air at 800 °C. The surface and interface morphologies of the coatings after isothermal oxidation after 100 h were observed and characterized by optical microscopy, field emission scanning electron microscope, energy dispersion spectrum, and X-ray diffraction. The results showed that the oxidation weight gains of the coatings were significantly lower than that of the low-carbon steel substrate. Moreover, the FeMnCrAl/Cr₃C₂-Ni9Al coating registered the lowest oxidation rate. This favorable oxidation resistance is due to the Al and Cr contents of the aforementioned coating that inhibits the generation of Fe and Mn oxides. This is attributed to the interdiffusion between the substrates and the Ni9Al arc-sprayed coating, which can convert the mechanical bonding between substrates and coatings into a metallurgical one, thereby inhibiting the oxidation of interface between the low-carbon steel and the coating.     

Effect of nano‐particulate sol–gel coatings on the oxidation resistance of high‐strength steel alloys during the press‐hardening process

The need for lighter constructional materials in automotive industries has increased the use of high‐strength steel alloys. To enhance passenger's safety press hardening may be applied to steel parts. However, as the steel parts are heated up to 950 °C during this process they have to be protected by some kind of coating against the intense oxide formation usually taking place. As the coating systems used so far all have certain disadvantages in this work the ability of nano‐particulate thin coatings obtained by the sol–gel process to improve the oxidation resistance of 22MnB5 steel is investigated. The coatings obtained from three sols containing lithium aluminum silicate and potassium aluminum silicate showed the best performance against oxidation. The structural properties of the coating materials were characterized using different methods like XRD and differential thermal analysis. Comparison of the oxidation rate constants proved the ability of the coatings to protect against oxidation at temperatures up to 800 °C. Press‐hardening experiments in combination with investigations on the thermal shock resistance of the coated samples also showed the ability of the coatings to stay intact during press hardening with only slight spalling of the coatings in the bending areas. The absence of any secondary intermetallic phases and layer residues during laser beam welding experiments on coated samples proves the suitability of the nano‐particulate coatings for further industrial processing.     

High-temperature oxidation and thermal cycling of aluminum-electroplated stainless steels

An alumina coating, produced from the oxidation of an aluminum-electroplated deposit, improved the oxidation resistance in air of a ferritic, AISI-type 446 stainless steel, Fe-24Cr-1.2Al containing 0.15% of mischmetal, and an austenitic AISI 321 stainless steel containing 0.53% Ti, at least up to 1100°C. In thermal-cycling tests from 1000°C to room temperature, the alumina coating was adherent on the ferritic and austenitic steels, for at least 1000 and about 700 cycles, respectively. The addition of rare earths to the ferritic steels and titanium to the austenitic, provided good adhesion between the coating and substrate. The porous nature of the coating was found to be very beneficial by causing the coating to be more resistant to thermal and growth stresses. Oxidation mechanisms are discussed in the light of results obtained from the thermogravimetric tests and metallographic observations by SEM-ED analysis.     

High Temperature Performance of an FeAl Laser Coated 9Cr1Mo Steel

The isothermal high temperature corrosion behavior of an FeAl coating, coated on 9Cr1Mo steel through laser surface alloying, was studied in atmospheres of pure oxygen and O₂ + 1 %SO₂. The specimens were tested at 500, 600 and 700 °C for 4–100 h. The mass change of the specimens versus time of exposure was used to study the kinetics of oxidation. The coating degradation through interdiffusion of alloying elements between the surface layer and substrate was investigated by long-term oxidation tests in air. OM, SEM, FESEM, EDS and EPMA analyses were used to study the oxidation behavior of the intermetallic coating. The results showed excellent oxidation/sulfidation resistance of the coated material due to a negligible growth rate of the oxide scale. However, the coating was degraded because of the interdiffusion of Al and Fe atoms between the coating and substrate after prolonged exposure to elevated temperatures.     

High‐temperature corrosion behavior of some post‐plasma‐spraying‐gas‐nitrided metallic coatings on a Fe‐based superalloy

The objective of the present study is to propose a cost‐effective process for modifying commercially available coatings by gas nitriding using commonly available equipment and starting materials. Al–Cr and Ti–Al metallic coatings were deposited on Superfer 800H (Fe‐based superalloy) using a plasma spray process. Then the gas nitriding of the coatings was done in the lab and the parameters were optimized after conducting several trials on plasma‐sprayed‐coated specimens. Characterization and high‐temperature corrosion behavior of coatings after exposure to air and molten salt at 900°C were studied under cyclic conditions. Techniques like XRD, SEM/EDX, and X‐ray mapping analysis were used for the characterization of the coatings and analysis of the oxide scale. Both the coatings successfully protected the substrate and were effective in decreasing the corrosion rate when subjected to cyclic oxidation (Type‐I hot corrosion) at 900°C for 50 cycles in air and molten salt (a salt mixture of Na₂SO₄–60%V₂O₅ dissolved in distilled water). Based on the findings of the present study, the coatings under study are recommended for tapplications to super‐heater and reheater tubes of boilers and all those surfaces that face fireside corrosion, such as fluidized beds, industrial waste incinerators, internal combustion engines, gas turbines or steam turbines, to provide protection against degradation in these environments. The cost of the product/process is approximately Rs. 0.62 per mm² in case of Al–Cr coating and Rs. 1.86 per mm² in case of Ti–Al coating.     

Void formation and filling under alumina scales formed on Fe–20Cr–5Al based alloys and coatings,oxidised at temperatures up to 1200 °C

During the oxidation, in laboratory air, of thin foils of Fe–20Cr–5Al based alloys, voids were formed in the substrate beneath the outer protective alumina scale after times varying from 50 h at 900 °C to 10 min at 1200 °C. Once the substrate aluminium level had dropped below a critical value (≤0.5 wt%), it no longer sustained the alumina scale formation and, as a consequence, continuing oxidation resulted in the initiation and development of a Cr‐rich oxide sub‐layer formation. At the lower temperatures, the voids filled with chromia leading to a scallop‐shaped inner layer beneath the alumina scale. In contrast, at higher temperatures, the Cr‐rich sub‐scale layer was continuous. If the Fe–20Cr–5Al based alloys are deposited as coatings, for example as a compliant layer onto a stronger substrate, there is a risk that other elements (such as silicon) from the substrate may diffuse through the coating and influence the subsequent oxidation behaviour of the coating. In order to simulate this, sandwiches of Fe–Cr–Al and a silicon rich substrate were fabricated and tested over a range of oxidation temperatures. It was then found that the silicon did indeed diffuse through the Fe–Cr–Al layer and change the oxidation mechanism. The voids formed under the alumina were now found to contain silicon oxide rather than chromia, but the void filling mechanism also appeared to be different. With chromia filled voids the filling commenced from the alumina scale, with the oxide growing inwards, while the silica rich regions grew outwards into the voids from the substrate. Scanning electron microscopy and EDX analysis were used to follow these changes and those in other more complex situations. Detailed mechanisms for void and chromia sub‐scale formation and development will be discussed in the paper.     

(Ti,Al)N–Ni nanostructured coatings: Thermal stability,heat resistance,electrochemical behavior,and adhesive strength with a substrate

In this work, thermal stability and oxidation resistance at temperatures up to 800°C are studied for (Ti,Al)N–(8–10 at %)Ni coatings with a thickness on the order of 4 µm and a crystallite size below 20 nm, which have been prepared via ion–plasma vacuum arc deposition. The composition and structural characteristics of coatings remain stable during 1-h heating in vacuum of 10_–4 Pa at temperatures of 600 and 700°C. Heating at a temperature of 800°C leads to an increase in the crystallite size and a decrease in microstrains of a ceramic phase, which is accompanied by a reduction in the hardness of the coating from 51–53 to 31–33 GPa. The coatings are heat resistant up to 800°C and characterized by cohesive failure in scribing. The adhesive strength of coatings with a substrate exceeds 85 N. Studying electrochemical behavior reveals the high efficiency of (Ti,Al)N_0.87–Ni coatings in corrosion protection of cutting tools in acid and alkaline environments.     

Accelerated cyclic oxidation testing protocols for thermal barrier coatings and alumina‐forming alloys and coatings

The oxide spallation resistance of oxide scales and ceramic thermal barrier coatings is a key design factor for developing high‐temperature alloy systems. Determination of the lifetimes of such alloy and coating systems is highly desirable. However, as improved systems are developed, lifetimes become so long that the time required to test a system to failure becomes prohibitive. Therefore, reliable protocols for accelerated testing and lifetime prediction are needed. This paper describes two attempts at developing such protocols. The first involves modification of the NASA COSP model to predict cyclic oxidation behavior of alloys and metallic coatings and the incorporation of acoustic emission data into this model. The second involves use of an indentation technique to induce spalling of thermal barrier coatings (TBCs) after short‐term thermal exposures. The first effort involves using the COSP Model, developed at NASA, as the basis for the prediction of oxide spallation. Acoustic emission measurements are used in an attempt to obtain critical parameters in the model from short‐time experiments for a variety of alloys and coatings which rely on alumina scales for oxidation resistance. The model is then used to predict the lives of these alloys and coatings when subjected to cyclic oxidation at 1100°C. A principal concern with ceramic thermal barrier coatings (TBCs) used in gas turbines is their loss of adhesion during service, leading to coating spallation. In this paper, an overview is given of an indentation test for brittle coatings on ductile substrates which is used to quantify decreases in interfacial toughness of TBC systems due to cyclic high‐temperature exposures. The indentation test involves penetration of the TBC and the oxide layer below it, inducing plastic straining in the underlying metal bond coat and superalloy substrate. The indentation strains cause an axisymmetric delamination of the TBC and oxide layers. Measurement of the extent of the delamination, coupled with finite‐element modeling, provides a measure of the adherence of the coating. Test results are presented tracking the loss of interfacial toughness for EBPVD TBC systems cyclically exposed at 1100°C.     

Effect of hot-dip aluminizing on the oxidation resistance of Ti–6Al–4V alloy at high temperatures

Hot-dip aluminizing and interdiffusion treatment were used to develop a TiAl₃-rich coating on Ti–6Al–4V alloy. Interrupted oxidation at temperatures from 600 to 900 °C and isothermal oxidation at 700 and 800 °C of the coating were conducted. The coating markedly decreases the oxidation rate in comparison with the alloy at temperatures below 800 °C during the interrupted oxidation. The oxidation kinetics follows parabolic relations at 700 and 800 °C during the isothermal oxidation. A layered structure of Al₂O₃/TiAl₃/TiAl₂/TiAl/alloy from the outside to the inside forms after oxidation at 700 °C without changing the main body of the coating.     

Cyclic oxidation resistance of Ni–Al alloy coatings deposited on steel by a cathodic arc plasma process

The cyclic oxidation resistance of nickel-aluminide coatings deposited on steel using a cathodic arc plasma (CAP) process has been investigated. Our results show that nickel-aluminide films can be successfully deposited on carbon steel and stainless steel substrates by this process; NiAl₃ is the major phase in the deposited films. The thermal cycling behaviour suggests that such coatings can resist oxidation through physical blocking of oxygen, either by the coating itself or by the aluminium oxide scale subsequently formed in-service. Aluminium diffusion inwards to the substrate may also be beneficial to the thermal oxidation resistance. The coating protects stainless steel substrate materials at 500°C by transforming the NiAl₃ phase into NiAl, producing aluminium oxide on the open substrate surface. At 800°C, oxide flaking is suppressed by the trace amounts of nickel or aluminium which have partially diffused into the substrate.     

Oxidation of Slurry Aluminide Coatings on Cast Stainless Steel Alloy CF8C-Plus at 800 °C in Water Vapor

A new, cast austenitic stainless steel, CF8C-Plus (CF8C-P), has been developed for a wide range of high temperature applications, including diesel exhaust components, turbine casings and turbocharger housings. CF8C-P offers significant improvements in creep rupture life and creep rupture strength over standard CF8C steel. However, at higher temperatures and in aggressive environments such as those containing significant water vapor, an oxidation-resistant protective coating will be necessary to extend service life. The oxidation behavior of alloys CF8C and CF8C-P with various aluminide coatings were compared at 800 °C in air plus 10 vol% water vapor. Due to their affordability, slurry aluminides were the primary coating system of interest, although chemical vapor deposition and pack cementation coatings were also compared. Additionally, a preliminary study of the low-cycle fatigue (LCF) behavior of aluminized CF8C-P was conducted at 800 °C. Each type of coating provided substantial improvements in oxidation behavior, with simple slurry aluminides exhibiting very good oxidation resistance after 3,000 h testing in water vapor. Preliminary LCF results indicated that thicker aluminide coatings degraded high temperature fatigue properties of CF8C-P, whereas thinner coatings did not. Results suggest that appropriately designed slurry aluminide coatings are a viable option for economical, long-term oxidation protection of austenitic stainless steels in water vapor.     

Internal Oxidation–Nitridation of Ferritic Fe(Al) Alloys in Air

Exposure of undoped Fe(Al) and Fe(Al)+Cr ferritic alloys in laboratory air at 900–1,000 °C resulted in significant internal attack after 5,000 h, including oxides and underlying nitrides. In the most severely attacked alloys, kinetics based on mass gain and maximum penetration depth were linear; also, the deepest penetrations were a significant fraction of the specimen thickness, and were thickness-dependent. Little internal attack was observed at 700–800 °C where these compositions may be used as coatings. The extent of internal attack did not decrease with increasing Al or Cr content which may indicate that rather than classical internal oxidation this attack is related to the permeation of N through a defective external scale. No internal attack was observed in alloys doped with Y, Zr, Hf or Ti where the substrate-alumina scale interface was flatter.