Y2O3/CeO2改性的低温渗铝涂层制备和循环氧化性能研究

本文利用Y2O3/CeO2纳米颗粒替代部分Al2O3粉作为填充剂,在Ni基体上, 600℃低温渗铝10h,制备了Y2O3/CeO2改性的低温渗铝涂层。作为对比,采用相同的工艺在Ni基体上利用纯Al2O3粉制备了普通渗铝涂层。对比研究了Y2O3/CeO2是如何影响氧化铝的相变以及渗铝涂层的1000℃时的循环氧化性能。结果发现,Y2O3和CeO2对q-a相变具有不同的作用：Y2O3抑制?-Al2O3的长大,而CeO2促进?-?相变。与普通渗铝涂层相比,Y2O3/CeO2改性的渗铝涂层形成粘附性更好的氧化铝膜,提高了渗铝涂层的循环氧化性能。文中对Y2O3/CeO2是如何影响?-?相变以及渗铝涂层的循环氧化性能进行了分析。     

Microstructures of thin and thick slurry aluminide coatings on Inconel 690

Two slurry aluminide coatings are produced on the Ni-base super alloy Inconel 690 by applying two different thicknesses of the same slurry on to the 690 substrate, followed by a two-step heat-treatment. The resulting thin aluminide coating consists of a single layer of Ni-rich β-NiAl matrix containing few large Cr precipitates with a high P content. The thick aluminide coating has a precipitate free inner layer of Ni-rich β-NiAl. An outer layer of Al-rich β-NiAl with many α-Cr precipitates has formed as well. The present metallurgical characterization shows a significant influence of slurry thickness on the morphology and composition of the coatings formed during heat treatment.     

Comparison between field and laboratory steam oxidation testing on aluminide coatings on P92

Steam oxidation has become an important issue for steam power plants as operating temperatures increase from the current 550 to 600–650 °C. For the last 10 years several groups have been carrying out steam oxidation testing of both uncoated substrates and coatings in the laboratory. On the other hand, field testing results are very scarce. In this paper, a comparison of laboratory steam oxidation testing with field test results carried out by Alstom at the Kraftwerk Westfalen power station located in Hamm, Germany will be presented. Both slurry deposited aluminide coatings and uncoated P92 steel have been included in the study. Under steam (atmospheric pressure) and isothermal conditions in the laboratory at 650 °C, spallation of oxides formed on ferritic steels occurs after significantly longer time when compared to exposure to real operating conditions. Oxide spallation results in serious damage in steam power plants by obstructing heat exchanger tubes, erosion of valves and turbine blades, etc. Moreover, the thickness of the oxide scales formed under field testing conditions is significantly higher after similar exposure. On the other hand, aluminide coated P92, which exhibit thickness through cracks, have shown to be stable in the laboratory for up to 60 000 h at 650 °C under steam, without evidence of crack propagation. However, field test results indicate that some degree of crack propagation occurs but without causing substrate attack up to 21 700 h of exposure. Moreover, the aluminium oxide observed in both laboratory and field tested specimens is different.     

Structure and cyclic oxidation resistance of Pt, Pt/Pd-modified and simple aluminide coatings on CMSX-4 superalloy

The coatings were prepared by the means of Pt and Pt/Pd galvanizing, followed by vapor phase aluminizing at 1050 °C. Microstructural and phase analysis revealed that all the investigated coatings consisted mainly of β-NiAl phase, however the Pt-modified aluminide coating also contained PtAl₂ phase and pure platinum precipitates. The cross-sectional microstructure of the coatings was zonal and composed of β-NiAl phase zone and the diffusion zone. The Pt modified aluminide coating's cross-section also incorporated an outermost zone consisting of β-NiAl and PtAl₂ phases. The concentration profiles proved that both Pt and Pd contents decrease gradually inwards the modified coatings. Cyclic oxidation tests at 1100 °C proved that Pt/Pd-modified aluminide coatings exhibit the best performance under cyclic conditions. The analysis of oxidation kinetics curves showed that the course of simple aluminide coating's oxidation is slightly different from that of Pt- and Pt/Pd-modified aluminide coatings.     

Determination of the ductile to brittle temperature transition of aluminide coatings and its influence on the mechanical behavior of coated specimens

The ductility of various coatings deposited by chemical vapor deposition, pack cementation and slurry processes on Fe- and Ni-based alloys was characterized by indentation at room temperature. A hot indentation apparatus has also been developed to more rapidly determine the ductile to brittle transition temperature of coated specimens. Creep testing has been conducted on bare and coated alloy 230 (NiCrW) specimens at 800 °C with a significant decrease in creep life observed. Based on the observed failure of coated 230 specimens, the impact of coating ductility on substrate creep properties is discussed.     

Low-temperature formation and oxidation resistance of ultrafine aluminide coatings on Ni-base superalloy

Ultrafine aluminide coatings were successfully produced on Ni-18Fe-17Cr superalloy at 540-600 °C in a modified pack-aluminizing process. Repeated ball-impacts accelerated the formation of the aluminide coatings by a surface refining process, resulting in atomic diffusion occurring at a relatively low temperature. The effects of the operation temperature and the treatment duration on the formation of the coatings have been investigated. The coatings possessed a two-layer structure. The top layer, approximately 5 µm in thickness, exhibited equiaxial coarse grains and was dominated by NiAl₃, with small amounts of Fe₂Al₅ and CrAl₅. The bottom layer showed high density, homogeneous, ultrafine grains with diameters approximately 30-50 nm. High-temperature oxidation tests were carried out at 1000 °C. The oxidation kinetics and microstructure of the oxide scale were studied. The experimental results indicated that the coatings greatly enhanced the high-temperature oxidation resistance of Ni-18Fe-17Cr superalloy.     

Steam oxidation resistance and thermal stability of chromium aluminide/chromium hybrid coating on alloy steels formed at low temperatures

This study investigated the feasibility of forming a hybrid coating with a structure consisting of a top Cr-aluminide layer and an inner Cr layer on alloy steels by using a two step process: electro-Cr plating and then pack aluminising at low temperatures. The oxidation resistance of the coating so formed was tested in ultrasupercritical steam of 650 °C and 30 MPa. The factors affecting the oxidation kinetics of the coating were studied by comparing its oxidation behaviour with that of the pack Fe-aluminide coating tested in the same ultrasupercritical steam. The thermal stability of the coating at 650 °C was investigated by a series of isothermal annealing experiments in argon atmosphere. It was demonstrated that the outer Cr-aluminide layer of the coating can improve the steam oxidation resistance of the steel substrate. The inner Cr layer can function as an effective barrier preventing the outward diffusion of Fe from the steel substrate; it can also act as a buffer zone, substantially reducing the rate of the inward Al diffusion process.     

Identification of degradation mechanisms in coatings for supercritical steam applications

The development and qualification of coatings for materials used in modern steam power plants stems from the increased demand for higher efficiency, and hence higher operating temperatures. Within the EU funded project ‘SUPERCOAT’, several coatings, both overlay and diffusion type, were investigated. Seven different coatings are presented in this work. They included two commercially available HVOF coatings (Ni–20Cr and Ni–50Cr), an aluminium‐based slurry coating (IPCOTE), together with two further variations of this slurry coating containing sputter‐coated inter‐layers. An overlay slurry coating consisting of silica particles embedded in a matrix of alumina and chromia was also examined. The final coating to be investigated was a pack‐aluminised sample of P92. All the coating systems examined showed superior oxidation resistance compared to the 9%Cr steel substrate (P91 or P92) in extended exposures to a steam environment at 650 °C. However, in service component lifetime will be limited by degradation of the coating, therefore it is essential that the mechanisms controlling this behaviour are understood. This paper reviews several degradation mechanisms that have been observed during long‐term exposure of these coatings. The mechanisms that have been observed include depletion of active alloying elements, diffusion of aluminium into the substrate from the coating, formation of Kirkendall porosity and mechanical failure of the coatings. Examples of each of these mechanisms will be presented. Possible processing routes to avoid these degradation mechanisms will also be discussed.     

Investigation of steam oxidation behaviour of TP347H FG. Part 2: Exposure at 91 bar

Tube specimens of TP347FG were exposed in a test superheater loop in a biomass plant in Denmark. The specimens were exposed to surface metal temperatures in the range of 455–568°C, steam pressure of 91 bar and exposure duration of 3500 and 8700 hours. The oxide thickness and morphology was investigated using light optical and scanning electron microscopy. The oxide present on the specimens is a duplex oxide with an inner chromium rich oxide and an outer iron rich oxide. The inner oxide consisted of a primary iron chromium nickel oxide in the original alloy grain and a chromium rich oxide, “healing layer”, at the grain boundaries. This gave the appearance of uneven inner oxide and it was clear that the varying subsurface grain size affected inner oxide thickness, especially after longer exposure times. Longer exposure times from 3500 to 8700 hours resulted in increased pit thickness. Comparison of pit thickness revealed that increase of temperature from 455 to 525°C increases the oxidation rate, however a further increase in temperature did not result in thicker inner oxide presumably due to the formation of a better healing layer at grain boundaries. These results are compared with the previous paper where the pressure and temperature was higher. A thicker inner oxide is observed at the lower temperatures and pressures compared with higher temperatures and pressures. Reasons for this behaviour are discussed.     

Influence of dissolved oxygen concentration and exposure temperature on the steam oxidation behaviour of HR3C

ABSTRACT

Oxidation behaviour of an austenitic steel HR3C at 620～650°C for 1000?h in steam with two different levels of dissolved oxygen (DO), 20?ppb and 5?ppm, was investigated by gravimetry, X-ray diffraction and scanning electron microscopy. Results showed that mainly a single-layered (Cr, Mn)₂O₃ scale was developed. The oxide growth followed near-power kinetics and was accelerated with DO concentration and exposure temperature. At the higher DO concentration, the formation of (Cr, Mn)₂O₃ with a much smaller size was favoured. Besides, the oxide scale became undulated and interfacial voids formed. Higher exposure temperature resulted in the growth of the (Cr, Mn)₂O₃ crystals and the change of their morphology from acicular to granular. Fe₃O₄ nodules and Ni-Cr spinel occurred at 650°C/5?ppm DO. Related oxidation mechanisms were discussed.     

Creep and corrosion testing of aluminide coatings on ferritic-martensitic substrates

Pack and chemical vapor deposited (CVD) aluminide coatings on commercial ferritic-martensitic Fe-9Cr-2W steel are being investigated by creep and corrosion testing at 650 °C. Results from different coating thicknesses show that the coated region makes no contribution to the creep strength. The creep behavior of uncoated material was studied after various heat treatments to simulate the coating process and typical secondary heat treatments. Alternating creep and corrosion exposures showed little effect on the creep strength of uncoated material but coated materials became progressively weaker. The coatings were protective in wet air at 650 °C after creep testing.     

Impact specimen geometry on T23 and TP347HFG steels behaviour during steam oxidation at harsh conditions

Ferritic T23 steel and austenitic TP347HFG steel have been studied with an emphasis on understanding the impact of specimen geometry on their steam oxidation behaviour. The selected materials were tested over a wide range of temperatures from 600 to 750°C. The tests were carried out in 100% steam conditions for 1000 hours. The tests indicated that the ‘curved-shaped’ specimens show slower mass gain, scale ticking and void nucleation rates than ‘bridge-shaped’ specimens (with flat and convex surfaces combined). Furthermore, a bridge TP347HFG sample showed the formation of lower amount of flaky oxide at 750°C.     

Processing, repairing and cyclic oxidation behaviour of sol–gel thermal barrier coatings

Sol–gel Thermal Barriers Coatings (TBCs) are manufactured using the dip-coating technique optimised in terms of process parameters including sol formulation, rate of withdrawing and heat treatment. The specific mechanisms of sol–gel TBCs, deposited on either NiAl or NiPtAl bond-coated superalloy substrates, are described. The possibility to reinforce and stabilise the crack network formed during the heat treatment or the first oxidation cycles using supplementary dip-coatings and appropriate process parameters is investigated. It is shown that implementing this technique that can be further regarded as an attractive way for repairing TBCs, significantly improves the cyclic oxidation behaviour of the multi-materials systems.     

TiAl合金表面机械研磨渗铝涂层的制备及高温性能

利用机械研磨渗在TiAl合金表面制备了铝化物涂层。在600℃经过150 min的振动处理后,TiAl合金表面形成了约为30μm的涂层。该涂层均匀致密,Al和Ti元素沿涂层均匀分布。XRD分析表明该涂层的相结构为Al3 Ti相。在900℃下,经过300 h的循环氧化后,该铝化物涂层表面形成了一层连续均匀的Al2 O3膜,表现出良好的抗氧化和抗剥落性能。相比之下,TiAl合金空白样表面形成了分层结构的氧化层,主要由Al2O3和TiO2混合氧化物组成,因此表现出较差的高温性能。     

The isothermal and cyclic oxidation behaviour of two Co modified aluminide coatings at high temperature

The isothermal and cyclic oxidation behaviour of two Co modified aluminide coatings together with the simple aluminide coating were performed at 1000 °C and 1100 °C. All the three coatings show a much lower oxidation rate compared with the bare alloy. Results also indicate the addition of Co to the aluminide coating decreases the oxidation resistance slightly. It can be ascribed to that Co is easier to be oxidized than Ni at high temperature, and the Cr(W) rich phases which could act as a diffusion barrier are less in the coating with higher Co content.     

Preparation and characterization of electroless Ni-P-Fe3O4 composite coatings and evaluation of its high temperature oxidation behaviour

Ni-P coatings modified with synthetic magnetite were prepared by electroless technique from a Ni-P plating bath containing magnetite powder. The coatings morphology was studied by means of scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS). The corrosion resistance at room temperature of the Ni-P films modified with magnetite was evaluated by means of electrochemical impedance spectroscopy (EIS), where the composite films exhibited a better behaviour. The films resistance to high temperature oxidation was evaluated by cyclic oxidation tests, SEM/EDS and X-ray diffraction analysis (XRD), where the coating with iron oxides appears to be more protective.     

The role of Cr atom in the early steam oxidation of Fe-based alloys: An atomistic simulation

This study employed the density functional theory to capture the atomic-level dissociation processes of steam and investigate the ions migration on Fe(001) and FeCr(001) surfaces, revealing the role of Cr atom in the early oxidation. Various coadsorption structures with different steam-derived species have been systematically examined to find the most energetically favored surface site. The results showed that the steam dissociation on the alloy surface underwent two steps. First, H₂O molecule on the top site was dissociated into OH group and H atom, which further combined with metal atoms on the bridge site and hollow site. Second, the OH group was decomposed into O and H atoms, which moved to two adjacent hollow sites and generated an oxide. On further oxidation, the Fe atom migrated outward and formed an outer Fe oxide, whereas the Cr oxide could only grow inward as O atom passed through oxide. It was found that the presence of Cr atom on the surface was thermodynamically beneficial, which could promote steam oxidation. The Cr atom could effectively block ion diffusion across the oxide scale and protect the underlying substrate from further oxidation. These results were in good agreement with experimental observation.     

Microstructural,corrosion and mechanical behavior of two-step plasma electrolyte oxidation ceramic coatings

Plasma electrolytic oxidation (PEO) is considered as a cost effective and environmentally friendly surface treatment process for improving surface properties of light alloys. The formation of ceramic coatings on Ti6Al4V alloy was reported by two-step PEO process and its structural, electrochemical and mechanical properties with the coated samples were compared by one-step PEO process in an alkaline electrolyte. The structural properties were studied using field-emission scanning microscope (FESEM) and X-ray diffraction (XRD). Electrochemical studies were carried out using linear polarization method and in addition mechanical behaviors were investigated by means of Knoop microhardness and nanoindentation method. Results showed that the second step process resulted in an increase of both porosity percentage and average pore diameter on the surface. The two-step process resulted in a small increase of thickness from about 12.5 to 13.0 µm. Electrochemical test results showed that applying the second step resulted in the decrease of both polarization resistance from 1800.2 to 412.5 kΩ/cm² and protection efficiency from 97.8% to 90.5%. Finally, the nanoindentation results indicated that the PEO coatings became softer but more ductile after applying the second processing step in acidic electrolyte.