J Fail. Anal. and Preven.
DOI 10.1007/s11668-013-9741-y
CASE HISTORY—PEER-REVIEWED
Failure Analysis of Welded Radiant Tubes Made
of Cast Heat-Resisting Steel
Ali Reihani • Seyyed Ali Razavi • Ehsan Abbasi •
Ahmad-Reza Etemadi
Submitted: 19 March 2013 / in revised form: 16 August 2013
Ó ASM International 2013
Abstract Radiant tubes made of cast heat-resisting steels
were cracked after 4 years of operation at 1020 °C tempera-
ture in hydrocarbon cracking furnace. Optical microscopy of
the tubes showed that there was extensive precipitation and
intermetallic compound formation especially as brittle net-
works with progressive reduction in toughness and resistance
to thermal and mechanical stresses. SEM and EDS analysis
proved both decarburization and oxidation on interior and
exterior surfaces. Apart from cracking due to long-term
heating, the tubes experienced high temperature creep. HAZ
cracking after welding of cracked and/or creeped tubes due to
formation of brittle carbide networks was overcome by
localized solution heat treatment followed by fast dry air
cooling. Localized dissolution of carbide networks and
intermetallic compounds resulted in lower strain microstruc-
tures and enhanced resistance of parts to thermal and
mechanical stresses during repair welding. It is evident that
localized solution heat treating other than lowering strains can
cause the precipitates to be more uniformly and finely dis-
tributed. Fast dry air cooling rate after solution heat treating
and similar cooling after welding can help to control precip-
itation of carbides. Detailed non-destructive testing after
welding along with tensile testing proved that post-weld
cracking was controlled.
A. Reihani (&)  S. A. Razavi  E. Abbasi
Welding & NDT Section, Assessment, Integrity Department,
Arya-Sasol Company, Southern Pars of Special Zone,
Asaluyeh, Iran
e-mail: reihania@aryasasol.com
A.-R. Etemadi
Department of Materials & Metallurgical Engineering, New
Mexico Tech, 801 Leroy Place, Socorro, NM 87801, USA
e-mail: aretemadi@alum.sharif.edu; a.r.etemadi@gmail.com
Keywords Embrittlement  Cracks  Decarburization 
Heat-affected zone  Welding
Introduction
Ethylene is usually produced through the steam cracking of
feed stocks such as ethane, naphtha, or gas oil. The choice
of feed stock is an important economic decision as it
influences other costs as well. Subject to availability, eth-
ane is probably the best feedstock, as it has higher yield
and selectivity of ethylene than heavier feed stocks and its
processing is relatively simple, involving lower capital
costs. Steam cracking is an endothermic process leading to
the breaking up of large molecules into smaller ones. The
cracking process is carried out in long tubular reactors,
known as radiant tubes, which are placed vertically in a
large, rectangular gas-fired furnace. The furnace consists of
convection and radiation sections, where the feedstock first
enters the convection section so that the hot stack gas
preheats the feed before it enters the radiation section.
Typical inlet temperatures to the radiant tube range from
500 to 800 °C. At an intermediate point in the convection
section, steam is introduced and is preheated together with
the feedstock. Steam lowers the partial pressure of high-
molecular mass aromatics, reducing condensation reac-
tions; in addition, it contributes to the partial removal of
coke in the tubes. The radiant coil is directly heated by the
burners, heating the process gas to the cracking tempera-
ture, which ranges from 700 to 900 °C. The temperature at
the outlet of the radiant coil typically ranges from 775 to
885 °C (Fig. 1a). The reactor effluent is quickly quenched
to prevent further reaction; compressed; and sent to a
separation unit for the recovery of ethylene and other
123

products such as methane, ethane, propane, propylene,
butylenes, and gasoline [1–3].
Carbon generated by the above reaction is deposited as
adherent coke on the radiant tube wall. Adherent coke can
have two detrimental effects. First, it acts as a thermal
insulator which requires a higher tube wall temperature in
order to maintain the same gas temperature. Secondly, it
accelerates carburization attack of the tube material. Typ-
ically, about 60–65% of the ethane is cracked to avoid
formation of excessive amounts of coke. At intervals which
can vary from a few days to several weeks, adherent coke
is removed by shutting off the hydrocarbon feed and
passing air and steam through the coil. Such a process is
known as decoking [1].
Radiant tubes are made frequently from centrifugally cast
high alloy steels. Two main types of tubes are used in Arya
Sasol Company, Southern Pars of Special Zone, Persian Gulf,
including 4852 Micro and ET45 Micro with chemical com-
positions as specified in Table 1. Surface temperatures of 4852
Micro and ET45 Micro tubes were 625–675 and 830–840 °C,
respectively. These steels are classified as non-standard high
alloy cast steels and make use the carbide forming elements Nb,
Mo, Ti as ‘‘micro-alloy’’ strengtheners, W and Zr together with
non-carbide forming additions of Al, Cu, and Co to increase
strength and/or carburization resistance [4]. Silicon is used in
low levels to maximize creep resistance and rupture strength
and at high levels to enhance carburization resistance. Carbon,
which is used as strengthener, is reduced in some modifications
to increase the resistance to thermal fatigue and shock [5–12].
These coils are experiencing girth and longitudinal cracking as
shown in Fig. 1b, c, such phenomena have been investigated
repeatedly before in the literature [13–20]. After 4 years of
operation, tubes experienced relaxation and/or creep defor-
mation with 50–80 cm increase in length and touching of the
Fig. 1 Crack in tubes after
4 years of heating (a) schematic
representation of tube
performance, (b) girth crack,
(c) longitudinal crack compared
with a virgin tube
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J Fail. Anal. and Preven.
bottom of the furnace compared to 14 m original length. To
control and keep the cracking process minimized, elongated
tubes were cut and welded again. Tubes welded during ‘‘first
installation’’ by using GTAW and DIN 2535 and DIN 3545 as
filler rod (Table 2) [21, 22]. Argon with 99.99% purity was
used as backing gas for welding. Visual examination, pene-
trating liquid testing, and radiographic tests proved that there
were no initial and/or out-of-standard defects in the welds.
Unfortunately, cut and repair welded tubes after creep,
encountered cracking in the heat-affected zone (HAZ).
Background
To control and evaluate worst conditions, ET45 Micro tube
samples were investigated. Chemical composition after
4 years of operation showed that the main alloying elements
remained essentially unchanged. Both interior and exterior
surface microstructure changes were investigated.
Figure 2a, b shows microstructure of specimens after 4 years
of heating in an ethane cracking system. The microstructure
consists of carbide particles within grain boundaries and a
matrix of austenite (c) with some needle-shaped phases. The
structure of Cr–Ni and Ni–Cr cast steels must be wholly
austenitic or mostly austenitic with some ferrite, if these are
to be used for heat-resisting services [23–25]. Depending on
Cr and Ni content, the structure of these iron-base alloys can
be austenitic (stable), ferritic (stable, but also soft, weak, and
ductile), or martensitic (unstable). A fine dispersion of car-
bides or intermetallic compounds in an austenitic matrix
increases high temperature strength considerably. For this
reason, heat-resisting cast steels are higher in carbon content
than are corrosion resistant alloys of comparable Cr and Ni
content. By holding at temperatures where carbon diffusion
J Fail. Anal. and Preven.

Table 1 The chemical composition of referenced standard materials (wt.%)

C Mn Si Cr Ni Nb Ti Mo Fe

4852 Micro 0.44 1.97 1.13 25.12 34.38 1.03 0.24 0.03 Bal.
ET45 Micro 0.46 1.86 1.08 34.45 44.66 0.95 0.19 0.02 Bal.
HP–Nb–Ti (reference for 4852 Micro) 0.5 1 1 26 35 0.5 0.1–0.3  Bal.
30-45-Nb–Ti (reference for ET45 Micro) 0.42 1 1 34 45 1 0.1–0.3  Bal.

Table 2 The chemical composition of GTAW filler metals used for repair welding (wt.%)
C Mn Si Cr Ni Nb Ti Fe

DIN 2535 0.4 1.5 1.0 25.0 35 1.2 0.1 Bal.

DIN 3545 0.45 0.8 1.0 35.0 45.0 0.9  Bal.

is rapid (above 900 °C) carbon can diffuse easily in steel.

Fine carbides increase creep resistance and decrease ductil-
ity as well. Ductility is reduced when strengthening occurs.
In some alloys the strengthening treatments correct an
unfavorable brittle grain-boundary carbide network. How-
ever, such treatment is costly and in most cases may warp
casting parts with complex shapes. Prolonged exposure of
such alloys to temperatures higher than 900 °C leads to
formation of sigma (r) phase. Sigma is extremely brittle, and
if it forms a continuous phase with carbides at the grain
boundaries, it can cause dramatic fracture. Figure 3a, b
shows decarburized layer with depths about 280 and 129 lm
on the exterior and interior tube surfaces. This clearly can be
attributed to the combustion reaction and carbon depletion.
However, this reaction is a bit slower for interior surfaces
where in direct contact with the coke layer a balance can be
struck between carburization and oxidation reactions.
In the present work, microscopy techniques and mechani-
cal tests were used to identify the root cause of failure. Based
on the obtained results, heat treatment parameters were
modified for better ductility along with desired strength.

Failure Analysis

To identify the cause of failure, initially a number of tubes

made of ET45 Micro steel were selected from used spec-
imens exposed to 4 years of heating. Then, chemical
analysis, dimensional measurement, visual and fluorescent
penetrant (FP) inspection were performed on the parts. Fig. 2 Carbide networks formed in grain boundaries of base metal
parts after 4 years of heating (a) carbide networks, (b) same structure
in higher magnification [etchant: Glycergia]
Chemical Analysis
Mechanical Test
Chemical composition of the selected tubes and the cor-
responding standard composition are given in Table 1. It is To investigate the influence of prolonged heating on the
discernible that the samples are of similar composition to mechanical properties, the selected tubes were tested and
the reference parts. results are presented in Table 3; long-term heating and carbide

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 J Fail. Anal. and Preven.

the observed phases at the interior and exterior surfaces.

Figure 4a, b shows SEM micrographs of both surfaces.
Table 4 presents EDS data obtained for light and dark
phases in both surfaces. It is evident that dark phase con-
tains both Si and oxygen and light one mainly contains Cr
and oxygen. The higher oxygen content of the outer surface
can be attributed to higher oxidation potential around tubes
in the furnace. However, lower oxygen activity inside tubes
along with reducing potential due to the presence of H2 and
CO was effective on lower oxygen content in precipitates.

Problem Solving

The physical metallurgy of cast heat-resisting alloys is

quite complex since these alloys contain a mixture of
intentional additions for precipitate formation (Ti and Nb)
and oxidation resistance (Cr and Si). Not surprisingly, the
welding metallurgy of these alloys is equally complex,
since partitioning of these elements during solidification of
the fusion zone can lead to formation of eutectic-type
constituents and secondary phases that are not normally
observed in the base metal. In the HAZ segregation of
alloying elements to the grain boundaries can promote
liquation or precipitate formation that negatively influence
weldability and mechanical properties of welded speci-
mens. Thus, it is not surprising that pre-weld or post-weld
heat treating is often required to protect or restore prop-
erties of the weldments. The usual heat treatment of such
Fig. 3 Decarburized layer formed on (a) exterior, (b) interior alloys includes solution heat treatment followed by artifi-
[etchant: Glycergia] cial aging. Centrifugally cast tubes with about 0.4 wt.%.
carbon content are prone to post-solidification aging. Long-
Table 3 Mechanical properties of standard and used tubes after term heating at temperatures higher than 900 °C can
4 years of heating accelerate aging and as can be observed in previous sec-
Hardness, HBN UTS, MPa Elongation, % tion, completes the aging process at the expense of
ductility. There are two main heating processes accelerat-
Used tubes 215 392 5 ing embrittlement. First, prolonged heating and fusion
Standard properties 175 586 10 welding and secondly, welding followed by post-weld heat
treatment both leading to strain-age cracking (SAC) phe-
nomenon in welds. This form of cracking is most prevalent
precipitation resulted in higher hardness compared to virgin with the c0 . Ni3(Al, Ti), strengthened alloys and many of
cast tubes (215 vs. 170–180 BHN). Carbide networks formed in them, especially superalloys are considered ‘‘un-weldable’’
grain boundaries (Fig. 2a) caused accelerated fracture with because of this mechanism. This mechanism is derived
lower ultimate tensile strength (UTS) and elongation values. from the fact that both local strain and aging must occur
nearly simultaneously. The term should not be confused
Microstructure with the metallurgical phenomenon of ‘‘strain-aging’’
observed in steels. SAC has been studied extensively in
Microstructural changes and the most prominent mecha- various Ni-base superalloys [26]. It is generally agreed that
nisms leading to the formation of carbide networks were SAC results from low ductility in the HAZ accompanied by
described in an earlier section. A scanning electron high strain accumulation in the same region [27–30]. Such
microscope (SEM) was used to study microstructural reduction of ductility is associated with the development of
evolution in the specimens. Energy-dispersive x-ray spec- grain ‘‘stiffening’’ by hard carbides and intermetallic
troscopy (EDS) was employed to analyze composition of compounds. Most investigators attribute this to the

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Fig. 4 SEM micrographs of surface of tubes and precipitates formed
after 4 years of heating (a) interior, (b) exterior (these values are
obtained from un-normalized percentages, not normalized values)
combined effects of grain boundary and grain interior
precipitation [29]. This problem is most prevalent in the
HAZ adjacent to the fusion line and in some cases asso-
ciated with the partially melted zone (PMZ). Intragranular
precipitation, as occurs in tubes during long-term heating,
results in hardening of the grain interior leading to stress
concentration at the grain boundaries [31, 32].
The level of weld residual stresses developed would
depend upon heat input, component geometry, mechanical
properties of the material, and elastic stiffness of the
restraining elements. As with other materials, the residual
stresses in heavily restrained steel weldments are consid-
ered to be on the order of the yield strength for these
materials. As can be observed for the tubes, elongation to
fracture significantly decreased and this is the main cause
of HAZ cracking. For repair welding, DIN 3545 and DIN
2535 filler rods were replaced with UTP Cr–Ni–Mo–Co-1
SMAW welding electrode. It can be concluded that the
base metal should be soft to allow the stresses developed
during welding to be relaxed. Therefore, it was decided to
solution anneal the parts before welding. But, complex
shapes of radiant coils forced the use of local heating. A
marginal band of 150 mm on both sides of the joint faying
surfaces were heated locally to 1150 °C at the rate of
150 °C/h and held at 1150 °C for 90 min. Then the heated
area was cooled by dry air for 3 min to 400–500 °C, and
then cooled in atmosphere. To overcome and control
problems associated with welding heat input, the maximum
inter-pass temperature was controlled at 150 °C. Figure 5a, b
shows post-solution heat treating microstructure of base
metal for 200 and 150 mm distances from the joint faying
surfaces, respectively. As can be observed in Fig. 5a, the
carbide networks remained unchanged, indicating that
regions at 200 mm distance were not affected by the
heating cycle. On the other hand, Fig. 5b shows the border
between heated and unchanged areas. Partial dissolution of
the carbide networks was very effective in reducing
welding thermal or mechanical strains. It is evident that
localized solution heat treating other than lowering residual
stresses can cause the precipitates to be more uniformly
and finely distributed. Fast dry air cooling after solution
heat treating and similar cooling after welding can help to
control precipitation of carbides. In addition, care must be
taken to avoid producing sufficiently high thermal strains
to leave high residual stresses on cooling. Figure 6 depicts
the joint liquid/solid interface after welding. Areas located
in the immediate vicinity of the melt areas have the highest
heat input and higher fraction of carbide precipitation
(marked ‘‘a’’). But outer areas (marked ‘‘b’’) experienced
only partial precipitation with contributing role to ame-
liorate side effects of carbide networks formed at the joint
interface. Figure 7 shows the weld solidification structure
in the vicinity of the solid/liquid interface and inside the
weld pool. As previously mentioned, many heat-resisting
steels have been developed that contain significant amounts
of Nb as a strengthening element that is added to form NbC
phases for elevated temperature strength. Microstructural
evolution in the fusion zone is quite complex. Most com-
mercial Nb bearing alloys exhibit a three step solidification
process that consist of L ? c stage followed by
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 J Fail. Anal. and Preven.

Table 4 EDS data obtained for light and dark phases in both sur-
faces (these values are obtained from un-normalized percentages, not
normalized values)
Fe Si Cr Oxygen

Interior dark phase 0.74 1.9 87.75 2.45

Interior light phase  61.44  16.24
Exterior dark phase  1.59 79.61 3.55
Exterior dark phase  58.03  19.34

Fig. 6 Optical micrograph of joint interface showing precipitates

formed during welding (a) and partial precipitation (b) [etchant:
Glycergia]

Fig. 7 NbC and Laves phases formed at the joint interface [etchant:
Glycergia]

typically produce a loss in strength and can promote pre-

Fig. 5 Optical micrographs of base metal after localized heating
(a) outer region remained unchanged (arrows show carbide network),
(b) border of dissolved and unchanged microstructure [etchant:
Glycergia]
L ? c ? NbC and L ? c ? Laves reactions at the ter-
minal stages of solidification [26]. Figure 7 shows c/NbC
and c/Laves eutectic-type constituents that form in the
fusion zone. The Laves phase is an intermetallic compound
with a hexagonal crystal structure A2B stoichiometry
where ‘‘A’’ represents elements such as Ni, Fe, Cr, and Co
and ‘‘B’’ represents elements such as Nb, Ti, Si, and Mo.
These phases are generally to be avoided because they
mature failure. Loss in strength is promoted by depletion of
solid—solution strengthening elements from the matrix,
such as Cr, Mo, and W. Depletion of Cr from the matrix
can also reduce corrosion resistance. Early failure can
occur due to the high hardness and plate like morphology
of these phases that cause premature cracking and brittle
failure. Figure 8a, b shows the weld microstructure, and it
is observed that owing to the relatively fast cooling rate
experienced after welding, formation of carbide networks
similar to the joint interface or the base metal were avoi-
ded. Austenite is the only stable phase associated with
solidification temperatures at the Ni-rich end of Fe–Ni–Cr
system. The simultaneous presence of C and strong carbide
forming elements as Ti and Nb can lead to formation of
MC type carbides in the inter-dendritic regions at the

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J Fail. Anal. and Preven.
Fig. 8 Weld microstructure (a) scattered NbC films formed after
weld metal solidification, (b) same structure at higher magnification
[etchant: Glycergia]
Fig. 9 Hardness data obtained for various joint areas (in BHN scale)
terminal stages of solidification by eutectic-type reactions
involving c and MC phases. Figure 8a shows carbide films
formed at the grain boundaries. The same structure at
higher magnification and carbide films are shown in
Fig. 8b.
Figure 9 shows hardness data obtained for various joint
sections from weld metal to the base metal. The minimum
values obtained for the weld metal is attributed to higher
cooling rate and lower chance for carbide precipitation and
network formation along with a softer austenite matrix. The
gradual rise in hardness values obtained for the HAZ is
clearly due to lower efficacy of the solution heat treating
conducted to the 150 mm distance that was unable to dis-
solve all carbide networks and precipitates which act as
nucleation and growth points for precipitates formed dur-
ing the weld thermal cycle. The nucleating effects of these
areas are so clear that it created a HAZ area with higher
hardness values compared to the base metal. The most
attractive role of the solution treatment is to break up the
continuous carbide networks formed during prolonged
heating exposure of radiant coils, not exclusively reducing
hardness.
Because tubes are designed to operate in the high tem-
perature cracking process, it was decided not to perform an
aging cycle on tubes. So, tubes are expected to operate for
longer time before precipitation of carbide networks and
formation of girth and longitudinal cracks as shown in
Fig. 1a, b.
Detailed non-destructive testing after welding confirmed
that there were no cracks found both on the surface and
beneath the joints.
Conclusions
The high amounts of Nb, Ti, and Cr additions in heat-
resisting steels act as driving force for gradual formation of
intermetallic compounds and carbide networks during
prolonged heating cycles and subsequent formation of
cracks. Repair welding of highly creep strained steels
resulted in formation of cracks in the HAZ. Localized
solution heat treatment around joint faying surfaces fol-
lowed by dry air cooling caused discontinuities in carbide
networks and lowered stresses along with some changes in
precipitate distribution. Fast dry air cooling after solution
heat treating and similar cooling after welding resulted in
controlling precipitation of carbides. Softer austenitic
matrix containing the least possible amount of carbides and
intermetallic network helped to overcome thermal and
mechanical stresses of the weld heating cycle without
formation of cracks in the weld metal or HAZ.
Acknowledgments The authors would like to thank all staffs in the
Welding/NDT section, Assessment and Integrity Division of Arya-
Sasol Polymer Company, Southern Pars of Special Zone.
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