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Different wear-resistant coatings produced by physical vapour deposition (PVD) were characterized with the aid of cross-sectional transmission electron microscopy (XTEM). All coating systems were optimized by the producers and exhibited good properties with respect to their special applications. The microstructure, texture and chemical composition of binary and ternary systems produced by the arc process [TiN, CrN, Cr2N (Ti, Cr)N on steel substrates] and magnetron sputtering process [TiN, CrN on steel substrates, (Ti, Al)N on Si-substrate] were investigated. All coatings had a more or less columnar microstructure, which was interrupted by interlayers in some cases. Whereas arc coatings always did show some kind of substrate modification, the latter was not observed after magnetron sputtering. Electron diffraction normally revealed a mono-phase fcc structure, except at sites very near to the interface. Only for the systems CrN and (Ti, Cr)N were different additional phases observed at low nitrogen partial pressures.
Up to ~ 3 µm thick alumina coatings on corundum ceramic, sodalimesilica glass and Inconel718 were produced from mixtures of boehmite sols and corundum suspensions.
Transmission electron micrographs in combination with electron diffraction and energy dispersive X-ray spectroscopy served to identify crystallographic phases and to characterize the microstructure of the coatings. Using corundum ceramic as substrate the initially deposited boehmite transforms via transition aluminas to corundum while heating to 1200 °C. In the cases of glass and Inconel718 thermal treatments up to 520 °C and 1100 °C, respectively, cause diffusion of ions from the substrates into the coatings. Thus additional oxide phases were formed.
All coatings are free of cracks or delaminations and do not show any directed crystal growth.
Alumina coatings with differing phase compositions were deposited on Inconel-718 (IN-718) Ni-base
superalloy substrates using solgel processing. Mass gain measurements served for studying the oxidation
behavior of coated metal surfaces if exposed to 800°C and 900°C for up to 4000 h in static air. Itwas found, that
alumina coatings significantly reduce the oxidation related mass gain of IN-718 even after heating to 900°C
for 4000 h. Transmission electron microscopy (TEM) studies revealed diffusion of elements from the metal
substrate (IN-718) into the alumina coatings and to a much lower degree from the coating into the
substrate. These diffusion processes are greatly influenced by the phase composition of the coatings, especially
by the presence of alpha-alumina.
A way to increase the application range and the lifetime of metallic substrates is their protection by coatings. Here the effect of alumina coatings on common steel substrates having different Chromium content is examined. The background of the investigations is to expand the application possibilities of mechanically good steels to higher temperatures and corrosive atmospheres in the framework of the European project POEMA (“Production of Coatings for New Efficient and Clean Coal Power Plant Materials”) which was introduced to identify materials that can withstand the aggressive conditions arising during the oxyfuel process in modern coal power plants. This process is one possibility to reduce the CO2 emission by firing the coal in oxygen and recirculated flue gas.
Substrate materials were P92 (9% Cr), K44X (19% Cr), and HR3C (25% Cr). The alumina coatings were deposited by a sol-gel-process using boehmite, this is relatively simple and offers application possibilities for a wide technical range without special surface preparations. All samples were dried for 30 minutes at 650° C to remove the organic components and to start the crystallization process of the alumina. For P92 and HR3C the following conditions simulated the oxyfuel process: 650°C in wet flue gas for 300h for the steel P92, the same conditions for 2000 hours for the steel HR3C. K44X was tested at 900°C in laboratory air for 500 hours. As well after drying as after testing TEM characterizations were performed, where the interfaces between steel and coating are of special interest to characterize the microstructure, detect failure mechanisms, and identify diffusion and crystallization processes and so to understand the mode of action of the alumina coating.
The TEM samples were prepared by the lift-out-technique using a FIB Quanta 3D and were investigated in a STEM JEM2200FS at 200kV.
After the coating and drying process all steels show chromium oxide layers directly at the steel surface, they vary in thickness and are island shaped in the case of the steel K44X. Chromium depletion arose more or less in the superficial zones of all samples. After the long term tests K44X showed breakaway oxidation while P92 and HR3C presented intact interfaces. This reveals: Beside the positive impact of the coating not only the Chromium content of a substrate is essential for the formation and self-healing of protective chromium oxide layers during the service time of steels. One has to consider the possibility of the steel to allow a continuously Cr diffusion to the interface and so e renewal of the Cr-oxide layer.
Inconel 718 was spin coated twice and fourfold with a sol to obtain 200- and 400-nm-thick transition alumina films on the surface. Bare and solgel alumina-coated Inconel 718 samples were exposed to NaCl solution to study their corrosion behavior by means of electrochemical impedance spectroscopy. In combination with scanning electron microscopy, it was shown that bare Inconel 718 is after initial passivation prone to pitting corrosion. For the coated Inconel 718 samples, an improvement in the protective effect of the coatings with time was observed. This observation is in contradiction to the results of other authors who observed degradation of alumina coatings exposed to NaCl solution with time. Transmission electron microscopy revealed a formation of (1) a compacted region at the coating surface as well as (2) a chromium-rich region at the interface between coating and alloy during the contact with a NaCl solution. The last one mainly contributes to the observed chronological sequence of electrochemical characteristics of the samples.
Microstructure, smoothening effect, and local defects of alumina sol-gel coatings on ground steel
(2017)
Porous alumina films with thicknesses of a few microns were prepared via a dip-coating technique on steel P92. The coating is shown to protect the steel against massive corrosion, which is typical in the hot reactive environment of coal fired power plants. To mimic real conditions ground steel plates were coated with a boehmite-sol. This leads to an overall smoothing of the formerly rough surface. In the following short annealing step the inner porous construction with worm-like particles consisting of nano-crystallites and amorphous alumina is formed. Due to the simultaneous diffusion of chromium and iron ions out of the bulk steel material into the porous alumina coating, a dense interface with satisfactory adhesion is formed. However, the film exhibits few local defects like cracks or dense alumina nodules caused by steep edges in the ground surface or agglomeration of boehmite-sol components, respectively. Cracks especially have to be avoided. This problem can be overcome so far by slight modifications in the sol preparation process and surface treatment of the substrates. Nevertheless the results demonstrate the potential of sol-gel based alumina coatings as a time- and cost-saving protection type for commercial steel P92.
1. Introduction
Alumina coatings are one possibility to increase the corrosion resistance, lifetime and application range of thermally loaded steel components, e.g. in modern power plants where the use of the Oxy-fuel technology corrosive fuel gas (H2O-CO2-O2-SO2 at 650 °C) affects the steel parts. In previous investigations the efficacy of protective alumina coatings on steel P 92 under those conditions was demonstrated. A shutdown and re-start of power plants or parts of them causes thermal stresses of the components which can cause detrimental effects like microstructural changes in the steel itself, changes in its oxidation behavior, delamination or microstructural changes in the coating. All those effects can lead to failure of the components, resulting in lifetime reduction.
2. Objectives
As a first step, we concentrate on the influence of thermal cycling tests and observe the impact on the microstructure of the coating and the interface in laboratory air. These investigations will help understanding the processes which occur, show directions of potentially necessary changes of the coating due to improved thermal stress behaviour.
3. Materials & methods
P 92 is a ferritic-martensitic steel, containing 9% Cr which forms protective Cr-oxide-rich scales in dry environments and non-protective ones in water-containing environments. Coupons of P 92, having ground surfaces, were dip-coated via a sol-gel process and subjected to thermal cycling for 500 h (1000 cycles) in laboratory air in a temperature range between room temperature and 660° C. The resulting mass loss was determined by weighing.
Samples for TEM investigations were produced as cross sections normal to the sample surface by FIB preparation (Quanta 3D, (FEI)). The TEM/STEM investigations were performed using a JEM2200FS (JEOL) operated at 200 kV. The microstructure of the coating and the interface after cycling tests was characterized via TEM, HREM, and STEM images, electron diffraction as well as EDX and EFTEM methods.
4. Results
At steep edges in the surface profile the coating was imperfect and cracks have formed during the thermal cycling. Flat surface regions are well-covered. The whole interface region between the steel and the coating shows a dense Cr-oxide-rich zone, which can form protective regions in case of local failure. The Cr-oxide zone is followed by a region of mixed oxides, containing Cr, Mn, Fe, and Al in variable composition, to which a porous δ-Al2O3 zone is joined.
5. Conclusions
• Alumina coatings promote the formation of dense, Cr-rich zones at the interface, which makes the system self-healing.
• These zones are stable during thermal stresses, even in regions with cracked coatings.
• They cause reduction of outward diffusion and mass loss during thermal cycling.
Thin Sol-Gel Alumina Coating as Protection of a 9% Cr Steel Against Flue Gas Corrosion at 650 °C
(2018)
Samples of sol-gel alumina coated and uncoated P92 steel were exposed to flue gas at 650 °C for 300 h. As result of this treatment a 50 µm thick bi-layered oxide scale had formed on the surface of the uncoated sample. Below the scale a 40 µm thick inner oxidation zone was detected. In contrast, the porous, micron thick alumina coating enabled the formation of a chromium oxide scale with a thickness of some nanometers at the interface between steel substrate and coating. In this case high temperature corrosion of the steel was prevented so far.