Proposed Metal Dusting Mechanism in Lowe

Paper No.
09161 2009
Proposed Metal Dusting Mechanism in Lower Temperature, High Steam Syn Gas
John J. Hoffman, Minfa Lin, William R. Watkins

Air Products and Chemicals, Inc.
7201 Hamilton Blvd.
Allentown, PA 18195
Sheldon W. Dean
Dean Corrosion Technology, Inc.
306 Marshall Landing
Glen Mills, PA 19342
ABSTRACT
Aggressive metal dusting attack of nickel-based alloys was encountered in high water vapor containing
syn gas environments in the 1000-1110oF (538-566oC) range while iron-based alloys suffered little
damage. Metallurgical and energy dispersive x-ray spectroscopy analyses of sectioned specimens
found the iron-based alloys formed protective chromium rich oxide films while the nickel-based alloys
did not. Nickel based alloys suffered both iron and chromium depletion from the surface layers as well
as accelerated attack. A mechanism for these observations is discussed.
INTRODUCTION
Metal dusting is an aggressive corrosion mechanism causing rapid disintegration of alloy surfaces. In
general, metal dusting occurs in carbonaceous atmospheres and is most severe in roughly the 950-
1300oF (510-705oC) temperature range. Despite being a subject of extensive research, the ability to
reliably predict alloy performance in various gas compositions remains elusive. The lack of knowledge
has caused some companies to intentionally avoid process designs that would result in operating in
potentially aggressive metal dusting environments, in important reforming and gas-to-liquids processes.
Thus, the fear of high metal dusting corrosion rates has, in some cases, resulted in less efficient, more
costly designs.
For the processes that proceed to plant fabrication, good engineering practice requires that one must
utilize the available literature to select the appropriate materials of construction. Laboratory studies, too
numerous to list, have been performed to compare metal dusting resistance of various alloys. The
cumulative laboratory test results indicate nickel-based alloys are more resistant to metal dusting attack
than iron-based alloys. Again, the fear of metal dusting drives many companies to utilize more
expensive nickel-based alloys in metal dusting environments.
Copyright
©2009 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE
International, Copyright Division, 1440 South creek Drive, Houston, Texas 777084. The material presented and the views expressed in this paper are
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1
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Recently, coupons exposed to syn gas environments (containing H2, CO, CO2, & H2O) stemming from
steam-methane reforming were evaluated. The performances of the plant exposed coupons were
consistently contrary to most lab test data. More specifically, iron-based alloys performed equal to or
better than most nickel-based alloys in the plant environments. The most notable difference between
the plant syn gas and the lab test gases was the water vapor concentration. Most lab test gases have
little to no water vapor while the plant syn gases can contain nearly 40% water vapor. This difference
provided the driving force for this paper, namely to assess the metal dusting resistance of iron- and
nickel-based alloys in actual plant environments containing typical levels of water vapor.
COUPON EXPOSURE RESULTS
Isothermal Coupon Exposure
Coupons were exposed in a plant syn gas stream (consisting of H2, CO, CO2) with >22% H2O at
approximately 1000oF (538oC) and 300 psig (2.07 MPa). A coupon rack was installed in 1999 and half
the coupons were removed after 12 months exposure. The remaining coupons were reinserted along
with a second coupon rack. The racks were removed providing coupons exposures of 12, 29, and 42
months. A third rack was inserted consisting of different alloys and removed after 13 months exposure.
The compositions of the alloys exposed are listed in Table 1.
Upon removal, the coupons were cleaned (ultrasonically in acetone) and weighed with the
corresponding mass loss/gain recorded in Table 2. As shown, the iron-based stainless steel alloys
performed equal to or better than many of the nickel-based alloys. The coupons were also mounted,
polished, appropriately etched, and examined via optical microscopy. In some cases, the coupon cross
sections were further examined in the scanning electron microscope (SEM) and energy dispersive x-ray
spectroscopy (EDS) employed for elemental chemical analysis of surface features and microstructural
constituents.
After 12, 29, and 42 months exposure, all the stainless steel alloys (SS; 304, 310, 347) including alloy
800H developed a thin (typically ~ 1 µm), adherent oxide film (Fig. 1). EDS analysis found this oxide
surface layer highly enriched in chromium (Cr) indicative of Cr2O3. The Cr2O3 layer proved to be highly
effective in mitigating carbon ingress into the base metal. A layer formed immediately below the
surface oxide layer that was much thicker than the oxide layer, typically 5-10 µm, that appears to be
white in the metallographic sections with EDS analysis indicating the layer was Cr depleted. Minor
carbon ingress was observed along grain boundaries and slip lines. The 310SS coupons had notable
sigma phase precipitation as expected at the exposure temperature (Fig. 2).
Optical microscopy of the nickel-based alloys was revealing. SEM/EDS analysis of alloy 600 in the as-
polished condition found the outermost layer to be essentially pure nickel with Cr-rich oxide underneath
(Fig.3). Etching indicated notable carbon ingress in and below the oxidized layer. Alloy 601 had similar
but less severe damage than alloy 600. The alloy 601 surfaces contained a Cr-rich oxide with
(essentially pure) nickel particles dispersed throughout the oxide layer (Fig. 4). At the base of the Cr-
rich oxide, aluminum (Al) enrichment was detected along the grain boundaries suggesting the onset of
an Al-rich oxide. The base metal below the oxide layer was chromium depleted. Etching found areas
of intermittent carbon ingress at apparent breaks in the surface oxide layer. The carbon ingress formed
a carbon-saturated band at the surface as well as grain boundary swelling (Fig. 5). The alloy 214 and
333 coupons again behaved similarly with EDS detecting Ni-rich particles on the surface and slight Cr
and Al enrichment at the exposed surfaces. However, the alloys tended to form intermittent oxide
surface films with notable carbon ingress at the disrupted areas. At many locations, the carbon
saturation formed the classic spherical segment shape in the base metal indicative of an imminent pit
(Fig. 6).
2
After 13 months exposure, the higher-alloyed Ni-based materials showed similar performance to the
alloys above. Alloy 617 had a heavy band of carbon ingress and grain boundary swelling essentially
identical to alloy 601 (see Fig. 5). Alloy 690 showed small, isolated areas of hemispherical carbon
ingress (as mentioned for alloy 333) but no metal loss or continuous carbon saturation of the base
metal. Interestingly, alloy 693, with composition essentially alloy 690 with a 3 wt% aluminum (Al)
addition, showed continuous carbon ingress along all exposed surfaces. The carbon ingress extended
0.010” (0.25 mm) below the exposed surface with a measureable microhardness increase (38 Rockwell
C average matrix hardness with hardness averaging 54 Rockwell C in the carbon-saturated band).
Alloy 602CA displayed the onset of occasional pitting with carbon ingress along the pit periphery (Fig.
7).
Variable Temperature Exposure
In a separate plant, 310SS and alloy 601 coupon rods (0.75” dia. bar) were exposed in an exchanger
for 2.5 years. The exchanger effluent syn gas (H2, CO, & CO2) contained > 22% H2O at 420 psig (2.90
MPa). The coupon rods extended down into the exchanger 234”. The exchanger is an up-flow design
with the syn gas cooling as it flowed up toward the top. Thus, the coupon rods allowed observation of
the effect of temperature on metal dusting. Down at the 234” elevation (top of exchanger being the
zero elevation point), the syn gas temperature was predicted to be approximately 1400oF (760oC). The
syn gas exits the exchanger at the 33” elevation at a typical temperature of 1050oF (566oC). The
temperature of the coupon rods is expected to change linearly between the 234” and 33” elevations.
The outlet nozzles are 13” ID with no temperature change expected in the 20”-33” elevation range.
Above the 20” elevation, the syn gas is expected to be highly turbulent with perhaps only slight cooling.
Once again, 310SS performed rather well in the high water vapor syn gas environment. Diameter
measurements, using a micrometer with pointed tips to measure in the base of metal dusting pits, were
taken along the length of the rod with the % diameter change listed in Table 3. Classic large diameter,
spherical segment pits were observed in the 16”-33” elevation range. The maximum metal loss
occurred at the 35” elevation with the surface in the 33”-55” elevation range being more textured with
small diameter pitting. In the 55”-96” elevation, the pits were very small diameter with little metal loss.
No measurable metal loss was found below the 96” elevation. Metallurgical cross sections were
prepared at various elevations of the rod and examined via optical microscopy. At the 20” through 55”
elevations, no surface oxides were present resulting in band of carbon saturation and deeper carbon
ingress along grain and slip boundaries (Fig. 8). Below the 96” elevation, the rod developed a thin
protective Cr-rich oxide surface film with the underlying Cr-depleted white layer (similar to Fig. 2).
Progressing down the length of the rod, the thicknesses of the oxide film and Cr-depleted layer
increased.
As shown in Table 3, the alloy 601 coupon rod suffered greater metal loss over a much wider
temperature range than the 310SS rod. Alloy 601 began suffering metal loss at the 8” elevation with
the maximum metal loss occurring at the 30” elevation. In the 8”-68” elevation range, the metal loss
produced a rather smooth, textured surface more typical of a general corrosion attack. In the 68”-150”
range, there was a high concentration of small diameter hemispheric pits. The pits grew to large
diameters, but fewer in numbered, in the 150”-208” elevation range. There was no measurable metal
loss below the 208” elevation. Optical microscopy was performed on numerous cross sections
prepared between the 20”-90” elevations. The microstructures from this elevation range were identical
with no protective surface oxide layers, a wide chromium depleted band, and carbide precipitation
below the chromium-depleted band (Fig. 9). In the 150”-208” elevation range, an extremely thin, Cr-
rich surface layer formed with large diameter pitting occurring at apparent defects in the surface layer.
Abundant carbide precipitation was observed in the microstructure with little evidence of a Cr-depleted
layer (Fig. 10). Below the 208” elevation, a protective Cr-oxide film formed with a notable underlying
Cr-depleted layer (Fig. 11).
3
DISCUSSION
Effect of Grain Size on Metal Dusting
The mass loss/gain data of the coupon exposures demonstrate the benefit of a fine grain size with
abundant grain boundaries to act as fast diffusion paths (see Table 2). The finer grained 304 SS and
347 SS alloys, ASTM grain sizes of 7 and 10 respectively, only contain 18 mass% Cr and performed as
well as the coarse grained 310 SS with 25 mass% Cr. This finding is consistent with published studies
on the oxidation resistance of 347 SS as a function of grain size1. In this study, fine-grained 347 SS
developed a dense, protective Cr2O3 layer while the coarse-grained 347 SS tended to form non-
protective iron oxide/spinel phases. Thus, the large grain boundary area resulting in the fine-grained
material provides a higher flux of chromium to the surface. The higher Cr flux in fine-grained materials
allows formation of protective Cr2O3 layers at lower bulk Cr contents as compared to coarse-grained
alloys.
The Ni-based alloys had similar grain size as the Fe-based 310 SS and alloy 800H but suffered notably
greater mass loss. The exception is alloy 600 having a grain size of ASTM 7 but the Cr content of only
15.5 mass% was insufficient to form a protective oxide film. The lower chromium content together with
the slower diffusion rate of chromium probably prevented the chromium oxide from forming a chromia
film, but rather encouraged the formation of a nickel iron spinel. In addition, the presence of
significant iron in the alloy (8%) encouraged the formation of a mixed metal spinel oxide, and that
depleted both iron and chromium from the surface layer. The nickel in the spinel crystals catalyzes the
formation of graphite whiskers that remove the oxide from the metal surface and allow further metal
loss to occur.
Effect of Aluminum Addition
The coupon exposure results showed little to no benefit of aluminum additions in the Ni-based alloys in
the temperature range studied. The aluminum diffusion rate appeared to be too slow to form protective
Al2O3 surface layers. Enrichment of aluminum was occasionally observed along the grain boundaries.
Aluminum will form Al2O3 at extremely low oxygen partial pressures as compared to Cr forming Cr2O3.
Thus, the inward diffusion of oxygen in the Ni-based alloys would form aluminum-rich oxides along the
grain boundaries. The formation of aluminum-rich oxides creates stress and eventual micro-cracking
along the grain boundaries 2,3. The grain boundary micro-cracking can lead to greater internal oxidation
and/or carburization of the base metal.
Fe vs. Ni Based Alloy Comparison
The metallurgical analysis confirmed that chromium is the alloy addition controlling metal dusting
resistance in both Fe- and Ni-based alloys. The observed differences in performance between the Fe-
based and Ni-based alloys are different from those published for environments with lower water
contents and oxygen partial pressures.
The coupon exposures consistently demonstrated that the nickel-based alloys experienced higher
mass loss/corrosion rates than iron-based alloys in the high water vapor containing plant syn gas
environments. The high water vapor content of the syn gas proved beneficial for the iron-based alloys
via formation of a protective chromium oxide film. This was not a surprise as the addition of steam to
syn gas has been employed to mitigate metal dusting for decades4. The apparent detrimental effect of
the high water vapor content on the performance of nickel-based alloys was a surprise. In addition to
differences in the water vapor concentrations, the carbon activities of the plant syn gas environments
were notably lower than aggressive laboratory environments where nickel based alloys were found to
be superior to iron based alloys 5,6.
4
Cr Diffusion
The bulk diffusion of Cr in austenitic Fe and Ni is sluggish (10-35 & 10-38 cm2/s, respectively) in both
materials in the 1050-1100oF (566-593oC) range7. However, bulk Cr diffusion in Fe is three orders of
magnitude higher than in Ni.
Grain boundary diffusion rates are generally accepted to be significantly greater than bulk diffusion
rates8. It is speculated that Cr diffusion along grain boundaries may be faster in Fe-based alloys versus
Ni-based alloys. Likewise, surface diffusion rates are higher than bulk rates. However, in the case of
nickel alloys, the adsorption of CO and H on the metal surface probably interferes with the surface
diffusion of chromium hindering its ability to create layers of chromia. Because the surface diffusion
rates are slower in Ni-based alloys, the Ni-based alloys tended to suffer intergranular oxidation from the
inward diffusion of oxygen instead of forming a protective surface oxide layer.
Spinel Oxide Formation
The development of a pure nickel layer on the alloy 600 metal surface is significant. This suggests that
there is a mechanism that removes iron from the alloy as well as chromium; Fe and Cr are oxidized
while Ni is not. Both the nickel alloy and iron alloy examinations support the theory that spinel oxides
are formed during the metal dusting process, in addition to Cr2O3, as shown in Fig. 13. The oxygen
partial pressures in the gas phase are too low for a nickel spinel (NiCr2O4) to form. However, a mixture
of Fe and Ni spinel [(Fe,Ni)Cr2O4] can form in Ni-based alloys when the alloy contains Fe.
Thermodynamic data is not available to plot the mixed nickel, iron spinel in Fig. 13 but this spinel would
form a parallel line between the FeCr2O4 and NiCr2O4 lines.
In the case of iron alloys, a mixed nickel iron spinel ([Fe,Ni]Cr2O4) is likely in addition to FeCr2O4 spinel.
Having significantly greater nickel concentrations in the base metal, the mixed [Fe,Ni]Cr2O4 formed on
Ni-based alloys will be more highly doped with Ni than the mixed metal spinel formed on Fe-based
alloys. The development of such an oxide on the metal surface would explain the large chrome
depleted layer on these alloys. The development of such an oxide would allow the precipitation of
graphite on the surface of the oxide crystals at places where nickel atoms were present. As noted
above, the mixed spinel formed on Ni-based alloys will contain greater concentrations of nickel atoms
catalyzing greater graphite precipitation. The graphite would tend to diffuse towards the metal where
the activity of graphite is lower and break the oxide off the metal surface.
A similar mechanism could occur on the alloy 601 except that the process would be limited by the iron
level in the alloy. The amount of (Fe,Ni)Cr2O4 spinel in Ni-based alloys is determined by the amount of
Fe content in the alloy. Ultimately, the surface layer would become devoid of iron as well as chromium
leading to a layer of almost pure nickel as we observed. Because the temperature is too low to allow
recrystallization, this layer would be porous and allow both oxygen and carbon to diffuse though it
readily resulting in the formation of chrome oxides, aluminum oxides, as well as carbides below the
nickel surface layer. It should be noted that a pure nickel layer would also encourage graphite whiskers
to form gradually removing the metal layer.
Carbon Activity and Oxygen Partial Pressure
The thick oxide film formed on the exposed coupons indicated that the oxygen partial pressure of the
syn gas is equally important as the carbon activity in terms of analyzing metal dusting. In the plant syn
gas environments, oxygen can be liberated via:
H2O å H2 + ½ O2 [1]
CO2 å CO + ½ O2 [2]
5
In a study by Nishiyama, et al 9, the surface oxide film thicknesses formed on alloy 800H were
measured after exposure to syn gas environments with varying H2O & CO2 concentrations. The
resulting oxide film thicknesses were plotted as a function of oxygen partial pressure calculated from
equation 1 and equation 2. The authors found the oxygen partial pressure calculated from equation 1
gave a better correlation to oxide film thickness. Thus, equation 1 must be considered in addition to the
carbon activity when assessing the aggressiveness of a syn gas environment. However, it should be
noted that this approach is incorrect because there can only be one oxygen partial pressure in a
system. The correct approach would be to determine an equilibrium gas composition with all of the
oxygen containing species, and calculate the oxygen partial pressure from that composition. In our
case, because the water vapor content is so high, changes to the water content from such equilibration
would be small, and consequently using equation 1 will give oxygen partial pressures that are very
close to the equilibrium value.
It is industry standard to calculate the carbon activity as a means to relatively assess the
aggressiveness of a syn gas environment. Plotting the carbon activity (as described by Dean10) as a
function of temperature for both plants in Fig. 12 and the plot of log oxygen partial pressure (Po2)
versus temperature for both plants in Fig. 13 provides an interesting observation. In both plant
exposures, the most severe corrosion occurred in the vicinity of 1000oF (538oC) implying metal loss is
accelerated by the competing oxidation and carburization mechanisms. The oxygen partial pressures
in the syn gas streams of both plants were more than sufficient to oxidize Cr to Cr2O3 as well as Fe to
the less protective FeCr2O4 and Fe3O4 but not high enough to oxidize Ni to NiCr2O4 spinel. In the
isothermal exposure, the Fe-based coupons developed protective Cr-rich oxides while the Ni-based
alloys suffered notable intergranular oxidation and metal loss. In the variable temperature exposure,
however, both the 310SS and alloy 601 rods were notably attacked in the roughly the 1050-1100oF
(566-593oC) temperature range. The Fe-based 310 SS, however, suffered less metal loss than the Ni-
based alloy 601. The key here is that high carbon activity occurs around 1000º F (538º C). As a result
the graphite formation is at a maximum rate catalyzed by nickel. The graphitization process involves
whisker formation and removes the nickel metal or nickel containing oxides from the surface
mechanically through the whisker growth process. In the case of iron based alloys, the lower nickel
content coupled with the higher chromium surface diffusion rate allows the formation of chromia on the
surface as well as spinel and ultimately the chromia creates a barrier layer to further accelerated attack.
High chromium containing nickel alloys, e.g., 25%, will also form chromia, although our results indicate
that they are less effective and thus suffer greater metal loss. It is also likely that the graphitization
process will undercut chromia crystals some of the time thereby removing them from the surface and
reduce the effectiveness of the chromia layer development.
In services where the carbon activity is high and the oxygen partial pressure is low, carburization is the
dominant mechanism for metal dusting attack. In this case carbon enters the metal and is available to
form carbides. Thus, Ni-based alloys would likely be preferred since Ni-based alloys have lower carbon
solubility and carbon diffusivity than Fe-based alloys. This is consistent with many published laboratory
studies utilizing gas environments with no water vapor. At higher oxygen partial pressures, the
environment is predominantly oxidizing and the less expensive Fe-based alloys appear well suited. It
should be noted, however, that the austenitic stainless steels (particularly 310 SS) suffer Cr depletion
via formation of a protective Cr oxide surface layers as well as precipitation of the Cr-rich sigma phase
(see Fig. 2). The simultaneous Cr depletion mechanisms could eventually lower the Cr content of the
matrix to < 12 wt% with potential for greatly accelerated metal dusting rates, as well as brittleness from
the sigma phase formation. Longer-term studies are on-going.
6
CONCLUSIONS
1) In syn gas environments containing high concentrations of water vapor, iron-based alloys
generally suffer less mass loss/gain than many highly alloyed nickel-based alloys.
2) Iron-based alloys developed protective Cr2O3 surface layers while the Ni-based alloys did not. It
is suspected that the formation of protective oxides implies the bulk and grain boundary
diffusion rates of chromium in iron-based alloys are higher than those in nickel-based alloys.
3) In the iron-based alloys, fine-grained material provided a large flux of chromium to the surface
allowing formation of protective Cr2O3 at bulk Cr concentrations considerable less than that
required for coarse grained material.
4) In nickel-based alloys, aluminum additions appear to result in the formation of aluminum-rich
oxides along the grain boundaries and eventual grain boundary micro-cracking. The grain
boundary micro-cracking can lead to greater internal oxidation and/or carburization. Iron and
chromium depletion also occurred in alloy 600 probably due to the formation of a mixed oxide
spinel that was carried away by graphite whisker formation.
5) In syn gas environments containing water vapor, both the carbon activity and oxygen partial
pressure must be considered to determine the appropriate materials of construction.
6) It is hoped that this work with stimulate laboratory analysis involving high water vapor syn gas
environments and the kinetics of nickel-catalyzed graphite formation to further validate these
findings.
REFERENCES:
1) Trindade, VB, Krupp, U, Hanjari, BZ, Yang, S, Christ H-J; “Effect of Alloy Grain Size on the
High-Temperature Oxidation Behavior of the Austenitic Steel TP 347”; Mat. Res. Vol. 8, No. 4,
Sao Carlos, Oct./Dec. 2005.)
2) Szakalos, P, Lundberg, M, Pettersson, R; “Metal Dusting on an Alumina Forming Ni-Based
Alloy”; Corrosion Science 48 (2006), p. 1679-1695.
3) Albertsen, JZ, Grong, O, Mathiesen, RH, Schmid, B; “Metallurgical Investigation of Metal
Dusting Corrosion in Plant-Exposed Nickel-Based Alloy 602CA”; Corrosion Eng., Science and
Tech., Vol. 40, No. 3, (2005), p. 239-243.
4) Perkins, RA and Coons, WC; Metal Dusting Corrosion in Coal Gasification Environments;
Electrochemical Society Inc. Proc., 77-1, 1976, p. 733-749.
5) Muller-Lorenz, EM, Grabke, HJ, and Zinke, M; Metal Dusting Resistance of Welded Nickel-
Based Alloys; EUROCORR 2001.
6) Baker, BA, Smith, GD; Alloy Selection for Environments Which Promote Metal Dusting; NACE
Corrosion 2000, Paper 00257.
7) Brandes, EA; Smithells’s Metal Reference Book, 6th Edition, Chapt. 13, Butterworths, Boston,
1983.
8) Grabke, HJ, et al; “Effects of Grain Size, Cold Working, and Surface Finish on the Metal-Dusting
Resistance of Steels”, Oxidation of Metals, Vol. 50, Nos. ¾, 1998.
9) Nishiyama, T., Kudot, T., and Otsuka, N.; Effect of Syn Gas Composition on Metal Dusting of
Alloy 800H in Simulated Reforming Gas Atmospheres; Corrosion, Jan. 2006, p. 54-63.
10) Dean, SW; “Estimating Metal Dusting Attack on Stainless Steel Alloys in Syngas Environments”;
NACE Corrosion 2001, Paper 01384.
7
TABLE 1 – Compositions of Exposed Alloys
(all values in wt%)
Alloy Cr Ni Fe Al Si Mo Other
304L 18 8 Bal - 1 -
347 18 8 Bal 1 - 1.1 Nb max
310 25 20 Bal - 1.5 -
800H 20 32 39.5 0.6 1 0.3 Al+Ti=1.2 max
600 15.5 72 8 - 0.5 -

601 23 60.5 13 1.3 0.2 -
617 21 54 1 1.2 0.1 9.5 12.5Co, 0.3 Ti
690 29 59 9 0.2 0.1 0.1 0.3 Ti
693 29 62 4 3.2 0.5 1.5 Nb, ? 1 Ti
602CA 25 62 9.5 2.3 0.1 - 0.13 Ti, 0.19 Zr, 0.09 Y
214 16 75 3 4.5 0.2 0.5 0.1 Zr, 0.01 B. 0.01 Y
333 25 45 18 - 1 3 3 Co, 3 W
TABLE 2 - Mass Loss/Gains from the Coupon Exposures

(all values in mg/cm2)
Alloy 12 Months 29 Months 42 Months 13 Months Grain Size

304L 0.28 0.27 0.51 7
347 0.23 0.31 0.46 10
310 0.20 0.23 0.41 5
800H -0.12 0.34 0.53 4
600 -139.46 -149.56 -312.38 7

601 -15.54 -1.83 -37.74 5
214 -9.90 0.25 -9.81 4
333 -87.28 -2.56 -42.46 5
617 -42.60 5.5
690 0.25 6
693 0.41 6.5
602CA 0.27 5.5
8
TABLE 3 – Coupon Rod Diameter Decreases along the Length
(zero elevation is at the top of the exchanger)
310 SS Alloy 601
Elevation Diameter % Dia. Change Diameter % Dia. Change
8" 0.75" 0 0.749" 0.13
16" 0.726" 3.20 0.711" 5.2
20" (1) 0.734" 2.13 0.702" 6.4
23" 0.736" 1.87 0.694" 7.47
25" 0.734" 2.13 0.680" 9.33
27" 0.655" 12.67
29" 0.723" 3.6 0.638" 14.93
30" 0.637" 15.07
31" 0.725" 3.33 0.641" 14.53
32" 0.642" 14.4
33" 0.722" 3.73 0.650" 13.33
34" 0.719" 4.13 0.661" 11.87
35" 0.703" 6.27 0.684" 8.8
36" 0.704" 6.13 0.694" 7.47
37" 0.718" 4.27 0.707" 5.73
38" 0.731" 2.53 0.718" 4.27
39" 0.740" 1.33 0.722" 3.73
40" 0.732" 2.4 0.720" 4
50" 0.745" 0.67 0.700" 6.67
60" 0.747" 0.4 0.700" 6.67
70" 0.748" 0.27 0.713" 4.93
80" 0.745" 0.67 0.697" 7.07
90" 0.748" 0.27 0.707" 5.73
100" 0.750" 0 0.717" 4.4
120" 0.750" 0 0.727" 3.07
140" 0.750" 0 0.728" 3.07
160" 0.750" 0 0.742" 1.07
180" 0.750" 0 0.748" 0.27
234" (2 ) 0.750" 0 0.750" 0
NOTES:
(1) Exchanger outlet temperature was 1050o F (566oC).
(2) Gas temperature at this elevation estimated to be 1400o F (760o C)
9
Fig. 1 – Micrograph of Alloy 800H after 42 month exposure (oxalic, 1000X)
(arrow indicates Cr oxide layer)
Fig. 2 – Micrograph of alloy 310SS after 42 months exposure (oxalic, 1000X)

(arrow indicates Cr oxide layer)
10
Fig. 3 – SEM micrograph of alloy 600 after 12 months exposure.
Fig. 4 – SEM micrograph of alloy 601 after 29 months exposure.
11
Fig. 5 – Micrograph of alloy 601 after 29 months exposure. (HNO3/HF, 200X)
Fig. 6 – Micrograph of alloy 333 after 29 months exposure. (HNO3/HF, 500X)
12
Fig. 7 – Micrograph of alloy 602CA after 13 months exposure. (HNO3/HF, 500X)
Fig. 8 – Micrograph from the 310SS coupon rod at the 35” elevation. (oxalic, 1000X)
13
Fig. 9 – Micrograph from alloy 601 coupon rod at the 40” elevation. (HNO3/HF, 1000X)
14
15
350
300
c 250
A
,y
itv 200
it
c Ac, Plant A

A
n 150
o Ac, Plant B
b
ra
C
100
50
0
900 1000 1100 1200 1300 1400
Temperature (deg. F)
Fig. 12 – Plot of carbon activity as a function of temperature for the two plant environments.
16
1.00E‐14
1.00E‐16
1.00E‐18
) 1.00E‐20
m
ta
( 1.00E‐22
e
r 1.00E‐24
u
ss Po2, Plant A
e 1.00E‐26
r Po2, Plant B
P
l 1.00E‐28
ai
tr 1.00E‐30 Cr2O3
a

P
1.00E‐32 FeCr2O4
n
e
gy 1.00E‐34 Fe3O4
x
O 1.00E‐36
NiCr2O4
1.00E‐38
1.00E‐40
1.00E‐42
800 900 1000 1100 1200 1300 1400 1500
Temperature (deg. F)
Fig. 13 – Plot of oxygen partial pressure as a function of temperature for the plant exposures
as well as the plots showing stability of various oxide and spinel phases.
(Thermodynamic data extracted from: F. Muller and O.J. Kleppa, J. inorg. Nucl. Chem. 35, 2673 (1973))
17

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Paper No.

John J. Hoffman, Minfa Lin, William R. Watkins

COUPON EXPOSURE RESULTS

Isothermal Coupon Exposure

Variable Temperature Exposure

Effect of Grain Size on Metal Dusting

Effect of Aluminum Addition

Fe vs. Ni Based Alloy Comparison

Spinel Oxide Formation

Carbon Activity and Oxygen Partial Pressure

600 15.5 72 8 - 0.5 -

TABLE 2 - Mass Loss/Gains from the Coupon Exposures

Alloy 12 Months 29 Months 42 Months 13 Months Grain Size

600 -139.46 -149.56 -312.38 7

Fig. 2 – Micrograph of alloy 310SS after 42 months exposure (oxalic, 1000X)

Fig. 4 – SEM micrograph of alloy 601 after 29 months exposure.

Fig. 6 – Micrograph of alloy 333 after 29 months exposure. (HNO3/HF, 500X)

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