Coke formation and metal dusting of electroplated Ni3Al-CeO2-based coatings in CO-H2-H2O

Coke formation and metal dusting of electrodeposited pure, 5 μm CeO₂-dispersed, and 9-15 nm CeCO₂-dispersed Ni₃Al coatings were investigated in CO-H₂-H₂O at 650 °C for a period of 500 h. All Ni₃Al coatings showed the inferior long-term resistance to coke formation and metal dusting to the Fe-Ni-Cr alloy due to failure to form a continuous Al₂O₃ scale. CeO₂-dispersed Ni₃Al coatings, especially 9-15 nm CeCO₂-dispersed coatings, exhibited more severe coke formation and metal dusting than the pure Ni₃Al coating. The detrimental effect of CeO₂ is believed to be caused by the enhanced formation of NiO/Ni crystals on the coating surfaces or at the grain boundaries, which catalysed the carbon deposition and promoted the carbon attack on Ni₃Al coatings.     

Cyclic oxidation of an ultrafine-grained and CeO2-dispersed δ-Ni2Al3 coating

A novel ultrafine-grained and CeO₂-dispersed δ-Ni₂Al₃ coating was fabricated through aluminizing a CeO₂-nanoparticle-dispersed nanocrystalline Ni matrix film using an NH₄Cl-activated pack cementation method at 600 °C. Two CeO₂-free δ-Ni₂Al₃ coatings, one coarse-grained and the other ultrafine-grained, were also prepared. Compared with the later, the ultrafine-grained and CeO₂-dispersed coating profoundly increased scale spalling resistance during cyclic oxidation in air at 1000 °C. The dispersed CeO₂, together with the ultrafine-grained coating structure, helped prevent the formation of cavities at the scale/coating interface, which was proposed as a main cause for improvement of the cyclic oxidation resistance.     

Discontinuous oxidation and erosion-oxidation of a CeO2-dispersion-strengthened chromium coating

A CeO₂-dispersion-strengthened chromium coating was developed on a carbon steel using a two-step process: prior electrodeposition of a Ni-CeO₂ nanocomposite film and subsequent chromization using a conventional pack cementation method. Compared to the CeO₂-free coatings prepared on the carbon steel without and with pre-electrodeposition of a pure Ni film, the CeO₂ dispersed chromium coating offered profoundly improved discontinuous oxidation resistance at 900 °C in 5% O₂ + N₂ and in 5% O₂ + 1000 ppm SO₂ + N₂, and erosion-oxidation resistance in a laboratory-scale fluidized-bed combustor (FBC), mainly because of the development of a denser, less wrinkled and more adherent chromia scale.     

Effect of pre‐oxidation on coke formation and metal dusting of electroplated Ni3Al–CeO2‐based coatings in CO–H2–H2O

Pre‐oxidation was introduced to improve the resistance of electroplated pure, 5 µm CeO₂‐dispersed, and 9–15 nm CeO₂‐dispersed Ni₃Al coatings to coke formation and metal dusting in 24.4%CO–73.3%H₂–2.3%H₂O at 650 °C. Coke formation and metal dusting of pre‐oxidized Ni₃Al‐based coatings were retarded up to 200 h owing to a thin Al₂O₃ scale induced during pre‐oxidation. The long‐term effectiveness of pre‐oxidation nonetheless depended on the integrity of Al₂O₃ scale. The pure Ni₃Al coating suffered severe spallation after pre‐oxidation and thereby showed the worst long‐term resistance. Two pre‐treated 9–15 nm CeO₂‐dispersed Ni₃Al coatings exhibited the best long‐term resistance to carbon attack because nano‐CeO₂ particles maintained a full coverage of Al₂O₃ scale on the coatings. Two 5 µm CeO₂‐dispersed Ni₃Al coatings showed significant spallation after pre‐oxidation because of an overdoping effect and experienced coke formation and metal dusting during long‐term exposure.     

Carburization Behavior of Electrodeposited Ni3 Al–CeO2-Base Coatings on Fe–Ni–Cr Alloys

The cyclic carburization of electrodeposited pure and CeO₂-dispersed Ni₃Al intermetallic coatings on Fe–Ni–Cr alloys has been investigated at 850 and 1050°C for periods up to 500 h in a reducing 2%CH₄–H₂ atmosphere. At 850°C, all Ni₃Al-base-coating samples showed excellent carburization resistance and slow mass increases due to the formation of a thin γ-Al₂O₃ scale and a low carbon activity (a _c = 0.73). At 1050°C and a high carbon activity (a _c = 3.21), all coatings are superior to the uncoated Fe–Ni–Cr alloy in terms of carburization resistance. A thin α-Al₂O₃ scale slowly formed on all Ni₃Al coatings effectively blocked the carbon attack. The addition of CeO₂ particles in the Ni₃Al coatings significantly mitigated the cracking of the α-Al₂O₃ scale and the resultant internal oxidation and carburization. For all coatings, Ni-rich particles were found to be formed on the α-Al₂O₃ scale during oxidation, which had led to the deposition of catalytic coke.     

Effect of alloying with Al on oxidation behavior of MoSi2 coatings at 1100 °C

MoSi₂ - 0, 15.3, 22, and 29.3 at.% Al coatings were prepared on the nickel-based super-alloy substrates by electro-thermal explosion ultrahigh speed spraying technology. The analysis showed that the coatings had fine microstructure with grain sizes ranging from 0.5 to 2 μm. The bonding between coating and substrate was typically metallurgical cohesion. The oxidation resistance of the coating was further studied at 1100 °C in air. Al alloyed in MoSi₂ coatings increased the oxidation resistance of the coatings, and the oxidation resistance of MoSi₂-15.3 at.% Al coating was higher than the other two MoSi₂–Al coatings. This suggested the oxidation resistance might have close relations to the obtained grain size.     

A novel ultrafine-grained Ni3Al with increased cyclic oxidation resistance

An ultrafine-grained (UFG) Ni₃Al was fabricated by annealing an electrodeposited Ni–Al composite in vacuum at 600 °C for 2 h. The UFG Ni₃Al, compared to a compositional-similar but coarse-grained (CG) alloy prepared by arc-melting, exhibited a greatly increased cyclic oxidation resistance at 900 °C. Microstructural investigation showed that the CG alloy grew a scale with a high susceptibility to buckling and cracking because of the formation of large voids at the scale/metal interface, but that the UFG alloy grew an adherent scale, because its typical structure prevented the formation of the interface void during oxidation.     

Ion-plated Al-Al2O3 films as diffusion barriers between NiCrAlY coating and orthorhombic-Ti2AlNb alloy

Ion-plated Al-Al₂O₃ cermet films were fabricated as diffusion barriers between NiCrAlY coating and orthhombic-Ti₂AlNb alloy. The oxidation and interdiffusion behaviour of coatings with and without diffusion barrier were investigated in isothermal and cyclic oxidation tests at 800 °C. The results indicated that substantial interdiffusion and rapid oxidation degradation occurred in the coated specimens without diffusion barrier. With Al-Al₂O₃ diffusion barriers, deferred interdiffusion and improved oxidation resistance was observed. Among them, duplex coating containing 1Al-Al₂O₃ interlayer exhibited the best performance. Coefficient of diffusion hindering and factor of reaction hindering were proposed to compare and quantify the efficiency of the diffusion barriers.     

Preparation and oxidation resistance of a crack-free Al diffusion coating on Ti22Al26Nb

A crack-free Al diffusion coating has been developed to improve the oxidation resistance of Ti22Al26Nb. It was produced by a two-step method; an Al film was deposited on the substrate alloy by arc ion plating followed by a diffusion process conducted at 873 K in pure Ar to form the Al diffusion coating. The two-step method lowers the temperature required to form the diffusion coating, which dramatically decreases the thermal stress developed in the coating and results in it being crack-free. The oxidation resistance of the non-coated Ti22Al26Nb alloy in isothermal and cyclic tests in air at 1073 K was poor, but the coated specimens possessed excellent oxidation resistance because a protective α-Al₂O₃ scale formed. The life of the Al diffusion coating greatly depends upon the rapid initial formation of a protective Al₂O₃ scale and interdiffusion between coating and substrate. Once the stable Al₂O₃ scale has formed and the composition changes from (Ti, Nb)Al₃ into (Ti, Nb)Al₂, the coating has a long life.     

Cyclic oxidation behaviour of Ti3Al-based alloy with Ni-Cr protective layer

The influence of a thin 80Ni-20Cr (at.%) protective coating on the cyclic oxidation of a Ti-24Al-11Nb (at.%) alloy based on Ti₃Al at 600 and 900 °C in air was investigated using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction analysis (XRD). The results of the oxidation tests showed that deposited Ni-Cr layer provides an improved oxidation resistance due to the formation of protective oxide scale which barriers the outward Ti diffusion into the scale. In some extent surface formation of the nitride layer also prevents diffusion of alloying elements from the matrix. Although oxidation at 900 °C is faster than that at 600 °C, a remarkable reduction in mass gain of the alloy with protective coating was observed. The thickness of oxide scale on the coated samples is approximately two times less than that formed on the uncoated samples treated under the same exposure conditions (120 h).     

Effect of cracking in diffusion aluminide coatings on their cyclic oxidation performance on Ti-based IMI-834 alloy

Diffusion aluminide coatings improve the high temperature oxidation resistance of Ti-alloys. This study evaluates the oxidation resistance of a Al₃Ti type aluminide coating and a Pt-aluminide coating on Ti-alloy IMI-834, at 650, 750 and 850 °C under cyclic oxidation conditions in air. Both coatings provide good oxidation resistance, however, the extent of through-thickness cracking in coating and localized oxidation degradation of substrate increases with thermal cycling. At high temperature of 850 °C, TiO₂ outgrowths emanate from these cracks, resulting in a prominent mud-crack pattern on the surface. The possible effect of such cracking on long-term oxidation properties of coatings has been discussed.     

The structure and high temperature corrosion performance of medium-thickness aluminide coatings on nickel-based superalloy GTD-111

Simple and Si-modified aluminide coatings having medium-thickness (40-60 μm) have been applied on the superalloy GTD-111 by a slurry technique. Hot corrosion and cyclic oxidation performance of the uncoated and the coated superalloy were investigated by exposing samples to a molten film of Na₂SO₄-40 %wt NaVO₃-10%wt NaCl at 780 °C and 1 h cyclic oxidation at 1100 °C in air, respectively. The presence of silicon in the aluminide structure increased the oxidation resistance by a factor of 1.7 times. In addition, a SiO₂-containing scale, which formed on the Si-containing coating surface, was stable during of the hot corrosion testing.     

Development and oxidation resistance of air plasma sprayed Mo-Si-Al coating on an Nbss/Nb5Si3 in situ composite

A Mo-Si-Al coating, which is mainly composed of Mo(Si,Al)₂ and Mo₅(Si,Al)₃, was developed to protect a Nb_ss/Nb₅Si₃ in situ composite by air plasma spraying. After oxidation at 1250 °C, the oxidation curve followed parabolic law and even after oxidation for 100 h, the weight gain of Mo-Si-Al coating was 8.24 mg/cm². The surface of the oxidized samples became flatter and smoother as time increased due to the formation of SiO₂ glass. Moreover, the microstructure of Mo-Si-Al coating changed and a layer structured interdiffusion zone was formed at the substrate-coating interface after oxidation.     

A fundamental aspect of the growth process of alumina scale on a metal with dispersion of CeO2 nanoparticles

The dispersion of CeO₂ nanoparticles resulted in a decrease of the oxidation rate of an ultrafine-grained Ni₂Al₃ at 1000 °C. The reason is explained as follows. During oxidation many Ce ions are released from the CeO₂ nanoparticles that are enveloped by the inward growing α-Al₂O₃ from the scale/metal interface due to an increased solubility. The Ce ions transport outward along grain boundaries of the scale, retarding the diffusion of Al ions for the thickening of the outer θ-Al₂O₃. This explanation is consistent with an observation that many CeO₂ nano-precipitates appeared mainly in the near-surface zone of the formed alumina scale.     

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.     

Structure and oxidation behavior of Si-Y co-deposition coatings on an Nb silicide based ultrahigh temperature alloy prepared by pack cementation technique

In order to improve the oxidation resistance of silicide coatings on Nb silicide based alloys, Y-modified silicide coatings were prepared by co-depositing Si and Y at 1050, 1150 and 1250 °C for 5-20 h, respectively. It has been found that the coatings prepared by co-depositing Si and Y at 1050 and 1150 °C for 5-20 h as well as at 1250 °C for 5 h were composed of a thick (Nb,X)Si₂ (X represents Ti, Cr and Hf elements) outer layer and a thin (Nb,X)₅Si₃ inner layer, while the coatings prepared by co-depositing Si and Y at 1250 °C for 10-20 h possessed a thin outer layer composed of (Ti,Nb)₅Si₃ and Ti-based solid solution, a thick (Nb,X)Si₂ intermediate layer and a thin (Nb,X)₅Si₃ inner layer. EDS analyses revealed that the content of Y in the (Nb,X)Si₂ layers of all the coatings was about 0.34-0.58 at.% while that in the outer layers of the coatings prepared by co-depositing Si and Y at 1250 °C for 10-20 h was about 1.39-1.88 at.%. The specimens treated by co-depositing Si and Y at 1250 °C for 10 h were selected for oxidation test. The oxidation behavior of the coating specimens at 1250 °C indicated that the Si-Y co-deposition coating had better oxidation resistance than the simple siliconized coating because the oxidation rate constant of the Si-Y co-deposition coating was lower than that of the simple siliconized coating by about 31%. The scale developing on the Si-Y co-deposition coating consisted of a thicker outer layer composed of SiO₂ and TiO₂ and a thinner SiO₂ inner layer.     

Cyclic Oxidation Behavior of Electrodeposited Ni3Al–CeO2Base Coatings at 850°C

The cyclic-oxidation behavior of electrodeposited pure, nano CeO₂ (9–15 nm)- and micron CeO₂ (5 μm)-modified Ni₃Al coatings on Fe–Ni–Cr substrates have been investigated at 850°C for periods up to 1000 hr. All the coatings showed good oxidation resistance in the early stage, but decreased oxidation protection during the intermediate stage of exposure. The formation of slow-growing γ-Al₂O₃ scales provided the coatings with good oxidation resistance in the early stage. However, a high volume fraction of pores in the coatings decreased oxidation resistance in the intermediate stage by forming oxidized channels between the pores. After long-term exposure, however, the pores in the coatings were healed by coating–substrate interdiffusion, and an improvement in cyclic-oxidation resistance was observed. The CeO₂ particles in the coating affected the stability of the protective oxide scale and the pore-healing behavior. The most significant effect was from nano size CeO₂ particles, which improved the stability of the protective oxide scale but retarded the rate of pore healing.     

Erosion of oxide scales formed on Cr3C2-NiCr thermal spray coatings

Cr₃C₂-NiCr thermal spray coatings are extensively used to mitigate high temperature erosive wear in fluidised bed combustors and power generation/transport turbines. The aim of this work was to characterise the variation in oxide erosion response as a function of the Cr₃C₂-NiCr coating microstructure. Erosion was carried out at 700 °C and 800 °C with erodent impact velocities of 225-235 m/s. The erosion behaviour of the oxide scales formed on these coatings, was influenced by the coating microstructure and erosion temperature. Development of the carbide microstructure with extended heat treatment lead to variations in the erosion-corrosion response of the Cr₃C₂-NiCr coatings.     

Formation of WSi2 coating on tungsten and its short-term cyclic oxidation performance in air

Microstructural aspects of WSi₂ coating on pure W and its short-term oxidation performance under cyclic heating and cooling conditions in air at 1100 and 1300 °C have been studied. Cyclic oxidation performance of this coating has been compared with its performance under isothermal oxidation. The coating was applied by using a pack siliconization method. The as-formed coating consisted of an outer WSi₂ layer and an inner W₅Si₃ layer. The WSi₂ layer had a columnar structure and had several through-thickness cracks generated due to the mismatch of coefficient of thermal expansion between the coating and the substrate. Based on the coating microstructure, the mechanism of coating growth during siliconizing has been suggested. Weight change data obtained under cyclic oxidation in air at 1100 and 1300 °C suggested that the above coating can provide protection to W substrate against oxidation for about 2 h. The oxide scale that formed on the coating during oxidation exposure consisted of SiO₂ and WO₃ at 1100 °C and only SiO₂ at 1300 °C. The protective silica layer underwent spallation during thermal cycling, leading to a diminishing of the protective capability of the coating. More importantly, localized oxidation of the W substrate through discontinuities present in the coating at sharp corners caused severe damage to the coated samples. Isothermal oxidation exposure of the coating, in comparison, resulted in a much lower degree of damage and the coating provided protection for a much longer duration (up to 10 h) at the above temperatures. In this study, apart from reporting a hitherto unreported oxide scale morphology, the microstructural degradation of the coating during oxidation has been linked to the columnar structure of the WSi₂ layer.     

Effect of lamellar microstructure on oxidation kinetics of Fe3Al sintered by hot isostatic pressing

The present paper focuses on the investigation of the relationship between microstructure of Fe₃Al prepared by hot isostatic pressing (HIP) and kinetics of alumina layer formation during oxidation at 900 °C, 1000 °C and 1100 °C. As prepared HIPed Fe₃Al sample reveals lamellar microstructure with inhomogeneous Al distribution which originates from the preliminary mechanical activation of Fe-Al mixture. At 900 °C, Fe₃Al oxidation is characterized by selective growth of very rough alumina layer containing only transient aluminium oxides. In addition to these transient oxides, α-Al₂O₃ stable phase is formed at 1000 °C. At the highest temperature (1100 °C), continuous and relatively smooth alumina layer mainly contains fine crystallites of α-Al₂O₃. The initial lamellar structure and phase inhomogeneity in as-HIPed Fe₃Al samples are supposed to be the main factors that determine observed peculiarities after Fe₃Al oxidation at 900 °C and 1000 °C.