Evaluation of a slurry applied aluminium coating for protection against steam side oxidation of ferritic and austenitic steels

A T Frya, D D Gohila, M Thompsonb, B McGheec

Rationale
There is a real need for process and material solutions for efficient, low emission power generation. Oxy-fuel combustion and the co-firing of biomass are two approaches being considered. Both will place the materials used under more arduous operating environments. With increasing cost of alloying additions and the need for higher temperatures and pressures for improved efficiency the use of coatings is becoming more attractive. Diffusion aluminide coatings are among the best performers and most cost effective of the possible processes available. As part of a UK Technology Strategy Board supported project on the Advanced Surface Protection to Enable Carbon abatement Technologies (ASPECT) the use of aluminium diffusion coatings has been assessed. This paper reports the results of the steam oxidation exposures conducted on the slurry aluminide coating.

Results
Uncoated substrates
At 650C in flowing steam, the uncoated ferritic steels T23 and T92 formed the typical oxide scales that would be expected, having a duplex microstructure. At 700 and 750C, the austenitic steels initially formed a thin chromia scale, which on longer exposure formed oxide scales of variable thickness consisting of an inner Fe-Cr oxide. Figure 2 shows the mean total oxide thickness as a function of the time1/2.

After 1000 hours exposure the intermetallic layer is still present, but is showing increased levels of attack. At the interface between this layer and the original specimen surface increasing amounts of Ni-Al intermetallics are seen to be forming, with increasing time these precipitates congregate at the grain boundaries, Figure 5. After 5000 hours at 700 C the coating is still providing an improvement in steam oxidation resistance compared to the uncoated substrate, Figure 6.

Experimental
Substrates
Five steel substrates were selected to represent a range of commercial grade tubing, shown in Table 1. These were coated on one of the major faces using an industrial slurry coating process by Monitor Coatings Ltd. In addition circumferentially welded tubes were coated internally to evaluate the performance of the coating on welded sections. Once coated the strips were cut into test pieces which were 10x15x4mm in dimension. The welded tubes were sectioned axially such that test pieces had a 20mm arc, 65mm long.
Alloy
T23 T92 Super 304H TP347H TP347HFG

Figure 2. Mean oxide thickness as a function of time1/2 for the uncoated ferritic and austenitic alloys.

Coated substrates
In the case of the ferritic materials, T23 and T92, the performance of the coating was disappointing, Figure3. For the T23 substrate after short exposure times of 100hours a relatively thick layer of iron oxide has formed which grows around the iron aluminide particles. As the exposure time increases the thickness of the iron oxide layer increases and the aluminium remains as discrete particles concentrated in a layer between the outward growing iron oxide and the substrate surface. For the T92 substrate there was initially a good protective layer of aluminium in the surface of the substrate, with the formation of iron and aluminium intermetallics. The aluminium of the coating combined with oxygen to form a thin discontinuous layer of iron aluminide intermetallic, which protected the T92 material up to 3000hours. After this it is observed to have broken down in places, which has allowed chromia to form around the aluminium rich region of the substrate, Figure 4.

Figure 5. Coated Super 304H after (a) 100h, (b) 1000 h, (c) 3000h and (d) 5000h at 700 C in flowing steam at atmospheric pressure

Figure 6. Uncoated Super 304H after 500h at 700 C in flowing steam at atmospheric pressure.

C
0.1 0.1 0.1 0.08 0.08

Si Mn

Composition, wt% Ni Cr Mo W Cu
2.6 9.5 18 18 18 0.3 1.75 0.6 2 0 0 0 0 0 0 0 0 3 0 0

V
0.03 0.25 0 0 0

Nb

Al

Fe

0.5 0.3 0 0 0 0.5 0.6 0 0 0.4 0.2 0.8 0 0 9 0.75 2 0.04 0.03 11 0.75 2 0.04 0.03 11

0.08 0.03 0.03 Bal. 0.09 0.04 0.07 Bal. 0 0 0.1 Bal. 0.82 0 0 Bal. 0.82 0 0 Bal.

Conclusions
Diffusion coatings offer a convenient method of providing additional surface protection to steam carrying tubes in high temperature plant. imple steam oxidation exposures on flat and welded tube S sectioned has demonstrated the level of protection this coating can provide. here is clear influence from the substrate material as T shown in the case of the low alloy T23, where the oxidation of the substrate progressed at such a rate that the iron aluminide nodules were simply bypassed by the outward growing iron oxide. here was clear benefit from the coating on the 9Cr ferritic T alloy but improvements are still required. urther modification of the heat treatment and delivery F method may improve the performance on ferritic alloys. he austenitic alloys were always going to exhibit T lower levels of attack, but as Figures 6 shows they are not immune and so would also benefit from surface modification such as that offered by a diffusion coating. continuous aluminium rich oxide was observed to form A on both substrates and welds giving protection from the internal attack shown on the uncoated materials, offering a mitigation solution to the early spallation of chromia scales on austenitic materials reported in the US. urther work is required to determine the resistance of the F coating and scales formed due to thermal cycling as this may limit the use due to the formation of cracks through the coating, the evaluation of the effect the coating has on the mechanical properties of the alloys is also required.
Queens Printer and Controller of HMSO, 2011. 10079/0512

Table 1. Nominal composition of the alloys in wt%

Coating
he slurry coating comprised of fine aluminium power T dispersed in a binder/carrier. Once applied the specimens were heat treated at 540C to cure the binder and encourage diffusion into the substrate. Once sectioned at NPL the specimens were subjected to a further heat treatment of 30 hours at 600C under argon to promote densification and formation of intermetallic phases within the coating (Figure1).
Figure 3. Coated T23 and T92 substrates after 100, 300, 3000 and 5000 hours at 650 C in flowing steam at atmospheric pressure.

Figure 1. Super 304H coated substrate after consolidating heat treatment.

Figure 4. Coated T92 substrates after 3000 hours at 650 C in flowing steam at atmospheric pressure.

Steam oxidation exposures

Samples were exposed to 100% flowing steam environments at 650, 700 and 750C for up to 5000hours. The feed water for the steam was deionised and deaerated. The level of dissolved oxygen within the feed water as a consequence was measured to be 10-15ppb. The specimens were exposed in a horizontal tube furnace with the water entering at one end of the tube, volatilising and passing over the samples before exiting the furnace. In contrast the performance of the coating on the austenitic alloys was encouraging. After the initial heat treatment an intermetallic layer can be seen across the surface which appears to be fairly continuous. After steam exposure some of the intermetallic layer is lost but the depth of the aluminium diffusion layer has thickened.

Acknowledgements
The research reported in this paper has been carried out as part of a UK Technology Strategy Board funded project Advanced surface Protection to Enable Carbon Abatement Technologies (ASPECT) (TP11/MFE/6/I/AA140E), with the support of E.ON Engineering, Cranfield Energy Technology Centre, RWE npower, Doosan Babcock Energy, Monitor Coatings, Sulzer Metco and Ceram Research. The Authors would like to express their gratitude to the UK Department for Business, Innovation and Skills.

National Physical Laboratory, Hampton Road, Teddington, Middlesex, TW11 0LW, UK b Monitor Coatings Ltd, Monitor House, 2 Elm Road, West Chirton Industrial Estate, North Shields, NE29 8SE, UK c Doosan Power Systems, Westway Business Park, Porterfield Road, Renfrew, PA4 8DJ, UK
a

tony.fry@npl.co.uk; dipak.gohil@npl.co.uk; m.thompson@monitorcoatings.co.uk; barry.mcghee@doosan.co.uk