Documente Academic
Documente Profesional
Documente Cultură
(2012) 1:199–207
DOI 10.1007/s13632-012-0036-6
TECHNICAL ARTICLE
Received: 17 August 2012 / Revised: 17 September 2012 / Published online: 13 October 2012
Ó Springer Science+Business Media New York and ASM International 2012
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200 Metallogr. Microstruct. Anal. (2012) 1:199–207
Additional strengthening is provided by solid-solution of technique in a solution of 30% nitric acid in methanol by
transition metals such as Nb in the case of HP–Nb steels volume. All foils were examined at an accelerating voltage
where the primary NbC carbides have been shown to of 200 keV. The stress-rupture tests were carried out at
assume a lamellar morphology [7]. 950 °C for up to 1000 h, and the results were extrapolated
A vertical catalyst tube (102 and 9 mm in internal to 100,000 h.
diameter) of a reformer furnace used in hydrogen produc-
tion developed a combination of corrosion and cracking
problem during the early stages of operation. According to Results and Discussion
design specifications, the tube was made of a grade of
HP–Nb heat-resistant steel casting on the basis of 100,000-h Table 1 shows the nominal composition of HP–Nb steel
service life. The tube was externally heated by means of used in the application in comparison with the results of
burners using a liquid by-product of a proprietary process chemical analysis by ICP-AES and CC. It is observed that
as a fuel and therefore, its composition could not be the measured composition is consistent with that of HP–Nb
specified. During operation, the tube temperature varied steel verifying that the tube was manufactured from the
from about 950 °C near the top to about 750 °C near the same steel as specified.
bottom, and as per specifications, the internal pressure was Figure 1a shows a schematic of a cross section of the
2.94 MPa (30 atm). However, after about 400 h of opera- furnace tube illustrating the orientations of the circumfer-
tion, a corrosion product continued to accumulate at the ential (r1) and longitudinal (r2) tensile stresses resulting
external surface particularly near the top. Also, ultrasonic from the pressure P exerted on the tube walls. A schematic
field testing revealed the presence of internal cracks. of the temperature distribution as provided by the propo-
Therefore, the tube was removed from service, and a sec- nent is shown in Fig. 1b. Light micrographs showing typ-
tion near the top was submitted for analysis to determine ical microstructures along the cross section of the tube are
the most probable cause of the observed damage. Also, shown in Fig. 1c–e. Evidence for corrosion attack is evi-
samples of the same material never used in service were dent at the outer surface, however, with the exception of a
included in the study. The present investigation was few localized pits, there was no marked thinning of the
undertaken to determine the cause of observed damage tube wall. Also, the maximum depth of the pits was
with emphasis on whether the corrosion attack could have observed to be about 80 lm as shown in Fig. 1c. However,
an adverse effect on the useful life of the tube and if there intergranular cracks were scattered along the entire cross
was also a correlation between the internal cracks and section as shown in Fig. 1c–e. As shown later, these cracks
corrosion attack. were found to be unrelated to the corrosion problem
observed at the outer surface.
As the ratio of tube internal diameter (di) to wall
Experimental Procedure thickness (t) is 11.3 [ 10, the stresses r1 and r2 in Fig. 1a
could be estimated on the basis of a thin-walled cylinder,
Specimens were machined from the as-received section of e.g., [8]. In this case, the maximum principal stress r1
the tube as well as the material never used in service to (circumferential stress) in Fig. 1a, which tends to produce
characterize their microstructures and also the stress- longitudinal rupture is given by: r1 = Pdi/2t = 16.7 MPa,
rupture life for the material never used in service. The which is to be compared with the 100,000-h rupture
chemical composition of the material was measured by
inductively coupled plasma atomic energy spectroscopy Table 1 Comparative chemical composition of HP–Nb steel (wt.%)
(ICP-AES) with the exception of carbon, which was mea- Element Nominal Measured Measured
sured by combustion calorimetry (CC). Various techniques (ICP-AES) (CC)
used to characterize the microstructure included light
Fe Balance Balance
microscopy, scanning electron microscopy combined with
Ni 23–25 24.37
energy dispersive x-ray spectroscopy, employing a win-
Cr 24–26 25.65
dowless detector, and transmission electron microscopy
Nb 1.4–1.8 1.71
and diffraction. To reveal the grain structure and primary
Si 0.5–1.5 1.42
carbides, metallographic specimens were etched in Mura-
Mn 1 (a) 0.36
kami’s reagent (10 g potassium ferricyanide, 10 g potas-
C 0.25–0.35 0.31
sium hydroxide, and 100 ml water). Specimens for
S 0.03 (a) 0.012
scanning electron microscopy were examined at an accel-
P 0.03 (a) 0.010
erating voltage of 20 keV. Thin foils for transmission
electron microscopy were prepared by the jet polishing (a)Maximum
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Metallogr. Microstruct. Anal. (2012) 1:199–207 201
strength of about 34 MPa at 950 °C as shown in the data of higher than normal operating pressure with no indication of
Fig. 2. Furthermore, the maximum localized thinning of significant creep damage.
the tube wall as a result of corrosion attack at the outer Typical microstructural features of HP–Nb steel never
surface (80 lm) as shown above amounts to an increase in used in service are summarized in Fig. 3. As shown in the
circumferential stress from 16.1 to 16.8 MPa, which still light macrograph of Fig. 3a, most of the grains assume
remains well below the inherent strength of the material columnar morphology. Primary carbides assuming lamellar
(Fig. 2). Therefore, up to the time the tube was removed morphology within the interdendritic regions of austenite
from service, the observed cracking could not be related to are shown in the scanning electron microscopy image of
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202 Metallogr. Microstruct. Anal. (2012) 1:199–207
Fig. 3b. A corresponding energy dispersive spectrum is concentration of Cr and smaller concentration of Ni as
shown in Fig. 3c illustrating that Fe, Ni, and Cr are the illustrated in Fig. 5c (region marked 2 in Fig. 5a) sug-
major elemental constituents with smaller concentrations gesting an oxide spinel of the type Ni(Fe,Cr)2O4.
of Nb and Si as expected. However, the microstructure of A typical microstructure along a cross section of the
tube was rather inhomogeneous. Some regions of the tube scale and into the substrate is illustrated in the backscat-
exhibited similar microstructural features to that of the tered scanning electron microscopy image of Fig. 6a
material never used in service as illustrated in the example showing that the tube material was subjected to internal
of Fig. 4a. The primary carbide was identified by micro- oxidation particularly along the grain boundaries. Also, the
chemical analysis and electron diffraction to be NbC (NaCl discontinuity of the outermost scale layer is noted as
structure with a = 0.447 nm). The elemental composition indicated by the arrow. Figure 6b shows the elemental
of the carbide is illustrated in the energy dispersive x-ray composition of the internal oxide consistent with Cr2O3-
spectrum of Fig. 4b. Figure 4c shows a dark-field trans- based scale. Previous studies have shown that internal
mission electron microscopy image of an NbC lamella. oxidation along grain boundaries is favored by large grain
Corresponding electron diffraction patterns consistent with size and relatively lower temperature favoring short-circuit
NaCl structure (B1-type superlattice) in [211] and [111] diffusion of oxygen along grain boundaries [9, 10]. It is
orientations are shown in Fig. 4d, e, respectively. How- noted that the scale contains a marked concentration of Si,
ever, as will be shown later, the microstructure in other which is known to increase the thermodynamic stability of
regions showed evidence for decomposition of primary Cr2O3 [11]. Also, within the detection limit of the tech-
NbC carbide during exposure at elevated temperatures. nique (about 0.2 wt.%), there was no evidence for incor-
Figure 5 is an example illustrating the morphology and poration of any impurities from the fuel such as chlorine
composition of the scale observed at outer surface of the into the oxide scale. Although internal oxidation can lead
tube. As shown in the secondary electron scanning electron to intergranular embrittlement [12], the effect appeared to
microscopy image of Fig. 5a, the scale has a porous be insignificant up to the time at which the tube was taken
structure. Also, spallation is noted at various locations out of service.
revealing the underlying scale layer. Figure 5b shows the Figure 7 shows a typical morphology and elemental
elemental composition of the outermost scale layer (region composition of the scale observed at inner surface of the
marked 1 in Fig. 5a) suggesting that it consists of Ni-rich tube. The morphology shown in the secondary electron
oxide containing Fe and a smaller concentration of Cr. In scanning electron microscopy image is typical of a pro-
contrast, Fe is observed to be the major metallic constituent tective layer of Cr2O3 with fine oriented grains consistent
of the underlying scale layer with relatively high with the composition shown in the energy dispersive x-ray
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Metallogr. Microstruct. Anal. (2012) 1:199–207 203
spectrum of the inset. Also, it appeared that the larger The above observations indicated that the environment
grains were formed from the smaller grains by shared created by burning the liquid fuel had precluded the outer
crystal faces. These morphological features are typical of tube surface from developing and maintaining a protective
Cr2O3 scale formed at temperatures in the range of surface layer of Cr2O3-based scale. Therefore, internal
900–950 °C [13, 14]. oxidation occurred faster than the rate of scale formation as
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204 Metallogr. Microstruct. Anal. (2012) 1:199–207
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Metallogr. Microstruct. Anal. (2012) 1:199–207 205
Fig. 8 An example
demonstrating the tendency of
the primary NbC carbide to
decompose during service into
Cr-rich carbide and Si-stabilized
Laves phase. (a) Backscattered
scanning electron microscopy
image illustrating the
co-existence of three phases
marked 1, 2, and 3; (b) energy
dispersive x-ray-spectrum
showing the elemental
composition of the phase
marked 1 in (a) suggesting a
Si-stabilized Laves phase of the
type Ni3Nb2Si; (c) energy
dispersive x-ray spectrum
showing the elemental
composition of the phase
marked 2 in (a) suggesting a
Cr-rich carbide of the type
M23C6; and (d) energy
dispersive x-ray spectrum
showing the elemental
composition of the phase
marked 3 in (a) suggesting
residual NbC carbide
stabilized by Si giving rise to a ternary phase of the type obvious that the precipitation of Laves phase had occurred
Ni3Nb2Si [20]. The Cr-rich phase 2 in Fig. 8a was identified during the earlier stages as indicated by its relatively small
as the Cr-rich M23C6 carbide (cubic structure) such as the amounts resulting in no significant creep damage as noted
particle marked 2 in Fig. 9a, and its corresponding electron earlier. It is also noted that decomposition of primary MC
diffraction pattern shown in Fig. 9c. It is well known that carbides at grain boundaries may leave behind unreacted
M23C6 carbide precipitated in high-temperature alloys ‘‘soft’’ zones of c-phase (solid-solution) alongside the
maintains a partially coherent relationship with the matrix boundaries [18]. These zones could act as loci for localized
phase with lattice constant three times that of the matrix plastic deformation providing another contributing factor
giving rise to characteristic reflections at every one-third to the observed cracking.
position of the matrix reflections [21] as shown in the [110]
diffraction pattern of Fig. 9c. Evidently, phase 3 in Fig. 8a
exhibiting white contrast corresponds to residual NbC carbide Conclusion
constituent with its composition shown in Fig. 8d. Therefore,
based on the above observations, the decomposition reaction Based on the results of this study, two sources for dam-
of the Nb-rich NbC carbide can be expressed as aging the furnace tube were identified, which could have
adverse effect on the useful life of the tube: (i) using a low-
NbC carbide þ matrix c-phaseðausteniteÞ
! Cr-rich M23 C6 carbide þ N3 Nb2 Si Laves phase grade fuel contaminated with highly corrosive species
accelerating the oxidation rate at the outer tube surface, and
As Laves phase is well known to be extremely hard and (ii) using a heat of the HP–Nb steel with Si content on the
brittle [20], its precipitation at grain boundaries could higher side of the specification stabilizing the extremely
contribute to the observed intergranular cracks. However, hard and brittle Ni3Nb2Si Laves phase precipitation of
at the time when the tube was removed from service, it is which at grain boundaries could contribute to intergranular
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206 Metallogr. Microstruct. Anal. (2012) 1:199–207
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