Metallogr. Microstruct. Anal.
(2017) 6:36–43
DOI 10.1007/s13632-016-0329-2
TECHNICAL ARTICLE
On the Degradation Modes of Various Steel Grades Used in Heat
Recovery Systems: An Application from the Petrochemical
Industry
H. M. Tawancy1
Received: 11 November 2016 / Revised: 14 December 2016 / Accepted: 15 December 2016 / Published online: 29 December 2016
 Springer Science+Business Media New York and ASM International 2016
Abstract Various steel grades used in the piping system of
a waste heat recovery system at a petrochemical plant
producing hydrogen by the steam–methane process are
shown to be degraded by different modes. Pipes made of
low-alloy steel (grade C-1/2Mo) have developed two
problems: (1) pitting and formation of a blackish powdery
deposit at the internal surface of the pipe adjacent to the
inlet of the reboiler, and (2) an oxide at the internal surface
of the bypass pipe fitted into a 304 stainless steel pipe.
Furthermore, a welded elbow made of 304 stainless steel
has developed a crack in the weld seam by a fatigue
mechanism. Although the results suggest that metal dusting
may be related to leakage of the reformed carbonaceous
gas into the piping system, a steel resistant to metal dusting
with a composition defined by %Cr ? 2%Si [ 24 wt%
may be considered for the application. On the other hand, a
steel with better fatigue resistance such as one with a
tempered martensitic structure may be considered as a
replacement for the 304 stainless steel.
Keywords C-1/2Mo steel  304 stainless steel  Metal
dusting  Oxidation  Fatigue
& H. M. Tawancy
tawancy@kfupm.edu.sa
1
Center for Engineering Research, Research Institute, King
Fahd University of Petroleum and Minerals,
KFUPM Box 1639, Dhahran 31261, Saudi Arabia
123
Introduction
Various grades of steels have long been widely used as
structural materials in the petrochemical industry due to
their potentially useful combination of engineering prop-
erties, availability and relatively low cost [1]. Examples of
applications include furnace tubes, piping systems and heat
exchangers. An important strategy in the petrochemical
industry to conserve energy, reduce operating cost and
enhance process efficiency is to install a waste heat
recovery system downstream in the process. For example,
it is estimated that fuel cost constitutes more than 90% of
the total cost required to operate a boiler system and that
about 10–20% of the input energy is wasted as heat con-
tained in the boiler outlet gases [2, 3]. Therefore, waste
heat contained in the outlet gases is transferred into the
feedstock of the boiler in the form of steam by means of a
piping system made of various steel grades.: It is noted
here that steam is a major source of energy for many
important industrial processes such as steam reforming,
which is defined as the process used to make various
products including ammonia, methanol and hydrogen from
natural gas. For example, hydrogen is produced from
methane according to the following reaction [4]
Methane ðCH4 Þ þ Steam ðH2 OÞ ! 3H2 þ CO
The above reaction occurs at high temperatures ranging
from 700 to 1100 C in the presence of a nickel catalyst. At
lower temperatures, additional hydrogen is produced in the
presence of an iron catalyst according to the following
reaction:
CO þ H2 O ! CO2 þ H2
Figure 1 shows a simplified diagram of the piping sys-
tem installed at the outlet of the boiler used in the
Metallogr. Microstruct. Anal. (2017) 6:36–43
Fig. 1 A simplified schematic illustrating the piping system of the
waste heat recovery system and the three locations where problems
have been encountered
production of hydrogen at a petrochemical plant. Accord-
ing to the plant documents, air is the environment outside
the piping system, and the reformed gas at the outlet is at a
temperature of about 845 C and consists of 74.6% H2,
13.6% CO, 9.1% CO2 and 2.7% CH4 by volume passing
through a 304 stainless steel pipe with 16-mm wall thick-
ness of an economizer unit where the heat content is
recovered by converting water into steam. This is fed into
the boiler by means of a piping system made of 304
stainless steel fitted with a bypass pipe with 16-mm wall
thickness made of a low alloy steel (grade C-1/2Mo) whose
function is to regulate the temperature by air flow. As
shown in Fig. 1, the stainless steel pipe is connected to a
pipe made of low-alloy steel with welded elbows made of
304 stainless steel. The steam is said to be delivered to the
boiler at a temperature of about 200 C. After an unspec-
ified period of operation, two problems were encountered
in the piping system connecting the economizer with the
boiler as illustrated in Fig. 1. On-site inspection revealed
the presence of pitting and a blackish powdery deposit
indicative of metal dusting at the internal surface of the
low-alloy steel pipe at the location marked 1 in Fig. 1, in
addition to a blackish deposit adhering to the surface.
Metal dusting is a form of severe high-temperature car-
burization which results in considerable metal wastage in
the form of powdery blackish deposits. This is to be dif-
ferent from carburization, which results in a blackish
deposit adhering to the metal surface. On the other hand,
another deposit adhering to the internal surface of the
bypass pipe, and believed to be an oxide, was detected in
the vicinity of the stainless steel pipe at the location
marked 2 in Fig. 1. Furthermore, a crack in the weld seam
37
at the internal radius of the stainless steel elbow was
detected at the location marked 3 in Fig. 1. Samples
removed from the three locations marked 1, 2 and 3 in
Fig. 1 were received for analysis to determine the under-
lying mechanisms leading to the observed damage.
Schematics of the samples illustrating the sustained dam-
age are shown in Fig. 2.
Experimental Procedure
Representative specimens were removed from the samples
shown in Fig. 2 for detailed chemical analysis and
microstructural characterization. To verify the alloys used
in the application, the chemical compositions of the
respective specimens were determined by the techniques of
inductively coupled plasma–atomic emission spectroscopy
(ICP-AES) and combustion calorimetry (CC). Optical
microscopy, scanning electron microscopy with micro-
chemical analysis using energy dispersive x-ray spec-
troscopy, x-ray diffraction and transmission/scanning
transmission (TEM/STEM) electron microscopy were
employed for detailed microstructural characterization of
the damaged pipes.
Specimens for optical microscopy were first ground
down to 600 grit using an abrasive disc and then polishing
with 9- and 3-lm diamond paste using nylon cloth fol-
lowed by etching in 3% nital solution. Scanning electron
microscopy (SEM) with energy dispersive spectroscopy
(EDS) experiments were carried out in a low-vacuum SEM
using the secondary and backscattered emissive modes as
well as the x-ray mapping mode, all at 20 keV using as-
received and polished specimens. X-ray diffraction exper-
iments were carried out on the powdery deposit using a
diffractometer with Cu-Ka radiation. The observed
diffraction patterns were indexed using x-ray powder
diffraction software. Ashes removed from the blackish
powdery deposit at v internal surface of the low-alloy steel
pipe (location 1 in Fig. 1) were also characterized by the
TEM/STEM modes of an analytical electron microscope.
The specimens examined were already transparent to
electrons at an accelerating voltage of 200 keV.
Results and Discussion
Material Verification
The results of ICP-AES and CC analyses in comparison
with the nominal chemical compositions of the low-alloy
and stainless steels used in the application are summarized
in Table 1. It can be seen that the compositions fall within
the specifications characterizing both alloys. Steels of the
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38 Metallogr. Microstruct. Anal. (2017) 6:36–43

Fig. 2 Schematic of the

samples removed from the three
locations in Fig. 1. (a) Sample
at location 1 in Fig. 1 with pits
and blackish deposit at the inner
surface of the low-alloy steel
pipe. (b) Sample at location 2 in
Fig. 1 with oxide at the inner
surface of the low-alloy steel
pipe near the 304 stainless steel
pipe. (c) Sample at location 3 in
Fig. 1 with a crack at the weld
seam of the 304 stainless steel
elbow

Table 1 Comparative chemical compositions (wt.%)

Element C-1/2Mo low-alloy steel 304 stainless steel
Nominal Measured Nominal Measured

Fe Balance 98.59 Balance 70.17

Cr … … 19 18.67
Ni … … 10 9.72
Mo 0.50 0.46 … …
Mn 0.55 0.52 2a 0.98
Si 0.30 0.31 1a 0.40
C 0.14 0.12 0.08a 0.06
a
Maximum

two grades are usually recommended for such applications

provided that the design specifications are followed during
service [1].

Analysis of the Damaged Low-Alloy Steel Pipes

Examination of the internal pipe surface at the location

marked 1 in Fig. 1 and schematically illustrated in Fig. 2a
has shown that the size of the pits ranges from macroscopic
to microscopic as demonstrated in Figs. 3 and 4. Figure 3a
shows a secondary electron SEM image along a cross-
section of large pits in the as-polished condition with
diameters ranging from about 1.5 to 3 mm and delineated
by a layer of deposit about 0.5–1 mm in thickness. The
morphology of the blackish deposit adhering to the surface
is shown in the secondary electron SEM image of Fig. 3b.
Figure 3c shows an EDS spectrum illustrating the charac-
teristic elemental composition of the blackish deposit
Fig. 3 Analysis of large pits and the deposit observed at the internal
surface of the sample shown in Fig. 2a (low-alloy steel pipe).
(a) Secondary electron SEM image along the cross-section showing
pits and a layer of deposit adhered to the surface as indicated by the
arrows (as-polished condition). (b) Secondary electron SEM image
showing the surface deposit (as-received condition). (c) EDS spec-
trum showing the characteristic elemental composition of the surface
deposit observed in (a) and (b)

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Metallogr. Microstruct. Anal. (2017) 6:36–43
Fig. 4 Analysis of small pits
observed at the internal surface
of the sample in Fig. 2a (low-
alloy steel pipe).
(a) Backscattered SEM image
of the internal surface (as-
received condition).
(b) Corresponding EDS
spectrum of the area in
(a) showing the elemental
composition. (c–(e) are x-ray
mapping images of Fe, O, and
C, respectively
adhering to the internal surface where C is seen to be the
major elemental constituent consistent with a layer of coke.
Figure 4 summarizes the results of analyzing the smaller
pits observed at the internal surface of the pipe in the as-
received condition. Pits about 5 lm in diameter can be
observed in the backscattered SEM image shown in
Fig. 4a. A corresponding EDS spectrum of the area in
Fig. 4a is shown in Fig. 4b where the major elemental
constituents are observed to be Fe and C with smaller
concentration of O. The corresponding x-ray mapping
images of Fe, O and C are shown in Fig. 4c, d, and e,
respectively.
The above observations indicate that the inner surface of the
pipe has been degraded by metal dusting. This is further con-
firmed by the results of x-ray diffraction analysis. Figure 5
shows an x-ray diffraction pattern obtained from the blackish
powdery deposit observed at the internal pipe surface as well as
standard diffraction patterns of cementite (Fe3C; orthorhom-
bic: a = 0.452 nm, b = 0.507 nm, c = 0.674 nm), graphite
(hexagonal: a = b = 0.247 nm, c = 0.680 nm), ferrite
(body-centered cubic: a = 0.287 nm) and magnetite (Fe3O4;
cubic: a = 8.39 nm). It is observed that most of the diffraction
maxima can be interpreted in terms of the structures of graphite
and cementite. Some ashes removed from the internal surface
of the pipe were found to be transparent to electrons at 200 keV
and therefore have been suitable for TEM/STEM analysis in
39
the as-received condition as demonstrated in the example of
Fig. 6. A bright-field STEM image of the ash is shown in
Fig. 6a. Corresponding microdiffraction patterns consistent
with the hexagonal structure of graphite in [001] and [1-26]
orientations are shown in Fig. 6b and c, respectively. As shown
in the EDS spectrum of Fig. 6d, C is the essential elemental
constituent of the ash, as expected.
Metal dusting is known to result from an aggressive
carburizing environment, which enhances the formation of
graphite and powders of metal carbides [5, 6]. Apparently,
there has been some leakage of the reformed carbonaceous
gas into the connecting pipe. On the other hand, metal
dusting is known to occur at temperatures in the range of
350–900 C. Therefore, it appears that the temperature at
location 1 in Fig. 1 has been higher than the normal tem-
perature, which is said to be about 200 C. Although the
exact mechanism of the metal dusting of carbon and low-
alloy steels is still subject to debate [6–10], it is believed
that the decomposition of cementite (Fe3C) into iron and
carbon may play a key role [7, 8].
In contrast with the damage sustained by the low-alloy
steel pipe at location 1 in Fig. 1, and described above, the
bypass low-alloy steel pipe near the stainless steel pipe
(location 2 in Figs. 1 and 2b) is found to be degraded by
oxidation, as summarized in Figs. 7 and 8. The morphol-
ogy of the oxide observed at the internal surface is
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40
Fig. 5 X-ray diffraction pattern derived from the powdery blackish
deposit removed from the internal surface of the sample shown in
Fig. 2a (low-alloy steel pipe) in comparison with the standard
diffraction patterns of cementite, graphite, ferrite and magnetite
illustrated in the secondary electron SEM images of Fig. 7a
and b. A corresponding EDS spectrum is shown in Fig. 7c
where Fe and O are observed to be the major elemental
constituent consistent with an iron oxide. This is further
illustrated in Fig. 8a showing a secondary electron SEM
image illustrating the morphology of the iron oxide along
the cross-section with a thickness ranging from about 25 to
40 lm. Cracks within the oxide are observed with evidence
of internal oxidation. A corresponding backscattered SEM
image is shown in Fig. 8b where the pearlite colonies can
be distinguished within the ferrite matrix. Figure 8c and d
shows the corresponding x-ray mapping images of Fe and
O.
It has been shown that a direct correlation exists
between the resistance to oxidation and resistance to car-
burization/metal dusting [11]. Therefore, to combat the
above problems encountered with the use of the low-alloy
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Metallogr. Microstruct. Anal. (2017) 6:36–43
Fig. 6 Identification of graphite in the powdery blackish deposit
observed at the inner surface of the sample shown in Fig. 2a (low-
alloy steel pipe) by TEM/STEM. (a) Bright-field image of ash in the
as-received condition. (b) and (c) are the corresponding microd-
iffraction patterns in the [001] and [1-26] orientations, respectively.
(d) Corresponding EDS spectrum showing the elemental composition
of the ash
steel, one of the alloys capable of developing more pro-
tective oxide layer, particularly Cr2O3, may be considered
for the application, e.g., an alloy in the class with a com-
position defined by %Cr ? 2%Si [ 24 wt%, such as alloys
800H and HK-40 [5, 6].
Analysis of the 304 Stainless Steel Elbow
Figure 9 is a secondary electron SEM macrograph showing
the major crack in the weld seam of the 304 stainless steel
elbow (location 3 in Fig. 1). It can be seen that the crack
follows a straight path with no evidence of branching.
Figure 10a is an optical micrograph of a polished and
etched specimen showing a sound region of a weld and a
heat-affected zone. However, at another location, a sec-
ondary transgranular crack is observed in the heat-affected
zone, which appears to extend from the external surface as
shown in the light optical micrograph of Fig. 10b. The
secondary electron SEM images shown in Fig. 11 illustrate
the morphology of the surface exposed by the major crack
in Fig. 9 as viewed at different magnifications. The stria-
tions observed in Fig. 11 indicate that fatigue has been the
crack propagation mode.
It has been reported that fatigue cracks in the weld
seams, such as that shown in Fig. 9, can start in the heat-
affected zone and extend into the weld seam due to the
combined effects of residual tensile stresses, heat-
ing/cooling cycles and vibration [12]. This appears to be
consistent with the observation of the heat-affected zone
crack shown in Fig. 10b; however, it has not been possible
to detect a crack extending from the heat-affected zone into
Metallogr. Microstruct. Anal. (2017) 6:36–43 41

Fig. 7 Analysis of the oxide

observed at the inner surface of
the sample shown in Fig. 2b
(low-alloy steel pipe). (a, b)
secondary electron SEM images
showing the surface
morphology of the oxide as
viewed at different
magnifications in the as-
received condition.
(c) Corresponding EDS
spectrum showing the elemental
composition

Fig. 8 Microstructural features

along the cross-section of the
oxide observed in Fig. 7 and
into the substrate (as-polished
condition). (a) Secondary
electron SEM image showing
the morphology of the deposit.
(b) Corresponding
backscattered SEM image
showing the pearlite colonies in
the ferrite matrix in the
substrate. (c) and (d) show
corresponding x-ray mapping
images of Fe and O,
respectively

the weld seam in the section of elbow received for analysis. martensitic structure [13]. However, a proper post-welding
A possible solution for the above problem is to use steel heat treatment of 304 stainless steel may also be considered
more resistant to fatigue such as that with a tempered as an alternative solution.

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42 Metallogr. Microstruct. Anal. (2017) 6:36–43

Conclusions

Fig. 9 Secondary electron SEM image showing the major crack in
the weld seam of the sample shown in Fig. 2c (welded elbow of 304
stainless steel)
The present study has shown that the low-alloy steel pipe
near the reboiler has been degraded by metal dusting
while the low-alloy steel pipe fitted in the stainless steel
pipe has been degraded by oxidation. Although leakage of
the carbonaceous reformed gas may have promoted metal
dusting, a replacement steel grade more resistant to oxi-
dation and metal dusting may be considered for the
application, such as that characterized by the composition
%Cr ? 2%Si [ 24 wt%. Cracking at the weld seam of the
elbow made of 304 stainless steel is found to occur by a
fatigue mechanism and, therefore, a tempered martensitic
steel may be more suitable for the application. On the
other hand, it is possible that a proper post-welding heat
treatment of 304 stainless steel could provide a solution to
the problem.

Fig. 10 Optical micrographs

showing characteristic
microstructural features of the
sample shown in Fig. 2c (etched
specimen). (a) Microstructure of
the heat-affected zone in the
vicinity of the weld. (b) A
secondary transgranular crack
observed at another location of
the heat-affected zone

Fig. 11 Propagation mode of

the weld seam crack observed in
Fig. 9. (a) Secondary electron
SEM image showing the
morphology of the surface
exposed by the crack; striations
characteristic of fatigue failure
can be observed. (b) Secondary
electron SEM image showing
the surface morphology at
higher magnification

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Metallogr. Microstruct. Anal. (2017) 6:36–43
Acknowledgment It is pleasure to acknowledge the continued sup-
port provided by King Fahd University of Petroleum and Minerals.
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