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A Higher Chromium Weld Overlay Alloy for Water Walls and Superheaters
By Larry Paul and Gregg Clark, ThyssenKrupp VDM USA Inc.
The coal-fired boiler environment produces corrosive conditions in both the furnace region and in the boiler convection pass. Corrosion-resistant weld overlay materials are widely used to manage these corrosion issues. In the furnace region, a mixed sulfidation/oxidation mechanism causes corrosion rates of up to 80 mpy (milli-inch per year) on boiler tubes (2 mm/y). The highest corrosion rates are seen where low NOX combustion is combined with burning high-sulfur fuels. This results in the formation of corrosive hydrogen sulfide (H2S) gases and ferrous sulfide (FeS) tube deposits. Higher chromium materials can support a protective chromium oxide scale even under severe conditions; therefore, they corrode less. The industry approach to date has been to restrict the chromium level of historical overlay materials to the upper end of their specification limits. One example of this approach is the common practice to restrict the chromium level of UNS N06022 (Alloy 622) to from 22.0 percent to 22.5 percent chromium (Cr), which is at the upper end of the specification limit of 20.0 percent to 22.5 percent chromium. This practice by its nature can only have a small influence on the level of chromium in the weld overlay and can only slightly increase corrosion resistance. Higher chromium contents in the weld overlay can be much more easily attained simply by switching to a higher chromium alloy. This was the basis for introducing Alloy 33 for use as a weld overlay on waterwall tubes in coal-fired boilers. Another concern in high pressure supercritical boilers is furnace wall tube cracking. This is a corrosion fatigue mechanism called circumferential cracking and has been observed on furnace tubes for many years. The root cause of this cracking is still under investigation by the Electric Power Research Institute (EPRI) and others, but higher design stresses, dirtier coals and running the boiler harder all make the problem worse. Some weld overlay materials have better resistance to cracking, but all materials have cracked under the most severe conditions. In the convection pass, coal ash corrosion can attack re-heater and superheater tubes. This corrosion mechanism involves molten alkaline iron tri-sulfate salt deposits on the boiler tubes and rates of 250 mpy (10 m/y) have been observed. Some recent studies suggest a mixture of mechanisms including oxidation, sulfidation and carburization may also now be involved. Recent changes in boiler operation to minimize NOX in the flue gas may be changing the corrosive conditions in the convection pass region and therefore the corrosion mechanisms. In convection pass tubes, the use of a high chromium weld overlay material has provided the best protection. FM-72, with 45 percent chromium, has been the preferred material to combat coal ash corrosion in convection pass tubes. Table 1 gives the nominal chemical compositions of the most common weld overlay materials now being used in coal- fired boilers.
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Alloy 33 Performance
Field testing was widely used to supplement laboratory corrosion data generated in earlier studies. Several sites were chosen to represent a wide range of boiler design and operating practice. The field tests were also used to evaluate the cracking resistance of Alloy 33, since the cracking mechanism is not fully understood, is quite complex and difficult to reproduce under laboratory conditions. Several boilers where circumferential cracking has occurred on other materials were intentionally selected to ensure a proper evaluation of Alloy 33s cracking resistance. The boilers used in the field testing are shown in Table 2 along with a description of the location and type of sample used.
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After five years, the corrosion resistance of Alloy 33 has been demonstrated in all of the boilers used in the test program. The corrosion rate of Alloy 33 has been less than 1 mpy in all cases. This is similar to the long-term corrosion rate measured in the laboratory studies for Alloy 33. Table 3 compares corrosion rates measured in the laboratory and field and projects the life of a weld overlay for Alloys 33 and 622. The laboratory measured corrosion rates are higher than those from actual boiler tubes, so the life projections in Table 3 are conservative estimates.
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Another goal of the field test program was to evaluate the resistance of Alloy 33 to circumferential cracking. After five years, there are no reported cases of cracking in any of the test panels. In one supercritical boiler, the Alloy 33 weld overlay sample was removed after 34 months and the tube panels bare ends were found to have circumferential cracks. While the SA213-T11 (1/ Cr- Mo) base tubing had cracks, the Alloy 33 weld overlay used on these same tubes was free from cracks. Cracks in the bare alloy tubes were about 0.020 (0.5 mm) deep and are filled with an oxide wedge with a sulfur spine down the middle; this is typical of circumferential cracking. Alloy 33 overlay directly adjacent to this area was investigated and found to be crack-free. Figure 1 shows micrographs of the cracks in the bare SA213-T11 tubing alongside the uncracked Alloy 33 weld overlay from this same region. Therefore, the Alloy 33 was shown to resist cracking even when in an area known to produce circumferential cracking. The same result was again observed in samples removed from this same unit in spring 2009. So, after five years of exposure in a supercritical boiler that has produced cracks in other boiler tube materials, the Alloy 33 remains unaffected.
Figure 1 Cross section of tubing samples The bare SA213-T11 tubes showed fairly deep circumferential cracks that are around 0.020 (0.5mm) deep. The Alloy 33 weld overlay directly adjacent to this region showed no evidence of cracking.
Approximately 8,000 square feet of furnace tubes were covered with Alloy 33 overlay at Western Kentucky Energy (WKE) in spring 2007. After two years of operation, the Alloy 33 is essentially unaffected and looks as good as the day it was installed. Several additional boilers have also used Alloy 33 weld overlay on the waterwall tubes (all field-applied so far).
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Alloy 33, which contains 33 percent chromium, clearly has sufficient chromium to impart excellent resistance to coal ash corrosion. In addition, Alloy 33 has excellent weldability and fabrication qualities.
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Figure 3 overlay tubes bent into superheater platens A 360 spiral overlay of Alloy 33 on a boiler tube. This is the weld overlay method used for superheater and reheater tubes. (Photo courtesy of Alstom Power.)
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holds a B.S. in marketing and business administration from the University of Illinois. More Power Engineerimg Issue Articles Power Engineerimg Issue Archives View Power Generation Articles on PennEnergy.com
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