Engineering Failure Analysis 16 (2009) 816–824

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Engineering Failure Analysis

journal homepage: www.elsevier.com/locate/engfailanal

Failure analysis of a welded outlet manifold pipe in a primary steam

reformer by improper selection of materials
Y.V. Nawancy *, Luai M. Al-Hadhrami
Center for Engineering Research, Research Institute, King Fahd University of Petroleum and Minerals, P.O. Box 1639, Dhahran 31261, Saudi Arabia

a r t i c l e i n f o a b s t r a c t

Article history: A welded manifold pipe in a primary steam reformer used to transport hydrogen gas at
Received 30 June 2008 about 873 °C developed leakage in the weld fusion zone after about 22,000 h of operation.
Accepted 2 July 2008 Detailed microstructural characterization using various electron-optical techniques and
Available online 10 July 2008
mechanical property evaluation were employed to determine the cause of failure. Selection
of pipe material and filler metal with relatively high Si contents in the presence of Nb was
Keywords: found to be the cause of failure. It is shown that this combination had promoted intergran-
Steam reformer
ular precipitation of the embrittling Ni3Nb2Si Laves phase in the weld fusion zone leading
Welded pipe
Leakage
to loss of rupture ductility and associated cracking.
Loss of ductility Ó 2008 Elsevier Ltd. All rights reserved.
Intergranular cracking

1. Introduction

In general, failure of engineering materials to perform their prescribed functions is expected to occur at the weakest link
in the inter-related processes of design, manufacturing, and service [1]. Therefore, among the most important requirements
of a material selected for a given application is its compatibility with the fabrication techniques used to manufacture hard-
ware items. For example, materials selected for applications involving fabrication by welding techniques must possess cer-
tain properties to maintain their structural integrity in the weld heat-affected zone.
Many structural applications in the petrochemical industry, e.g. steam reformer pipes, rely upon the use of heat-resistant
steels based Fe–Cr–Ni systems, which are selected on the basis of 100,000 h creep-rupture strength and carburization resis-
tance [2,3]. However, in most cases, the rate of carburization attack is rather low and can be ignored as a contributory factor
to failure [3]. Steels in this category derive their strength from carbide precipitates as well as solid-solution strengtheners
particularly heavy transition metals such as W, Mo, and Nb. Resistance to carburization attack is enhanced by additions
of P1% Si, [3,4]. Due to the lack of sufficient ductility, pipes used in reformer applications are produced by casting in lengths
up to 5 m and subsequently joined by welding to obtain the desired length.
It is well known that commercial bulk hydrogen is produced from natural gas by the catalytic steam reformer process,
which involves the cracking of methane. The process is carried out in units consisting of a reforming section usually contain-
ing seven vertical pipes welded to a common outlet manifold pipe assembled by welding. Process feed gas predominantly
consisting of methane is fed into the reforming section where it is cracked over a nickel-base catalyst. Products of the crack-
ing reaction mainly consisting of hydrogen pass through the manifold pipe.
Fig. 1a shows a schematic of the reformer unit. In the present case, the inlet and outlet gas temperatures were about 530
and 873 °C respectively, and the internal gas pressure in the manifold pipe was held at about 1.9 MPa (19 kg/cm2). Although

* Corresponding author. Tel.: +966 3 860 4317.

E-mail address: tawancy@kfupm.edu.sa (Y.V. Nawancy).

1350-6307/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.engfailanal.2008.07.001
 Y.V. Nawancy, L.M. Al-Hadhrami / Engineering Failure Analysis 16 (2009) 816–824 817

Fig. 1. (a) A schematic illustration of the steam reformer unit. (b) A schematic illustrating the location of the sample removed for the study.

Fig. 2. Macroscopic features of the sample removed for analysis in the as-received condition.

the pipe was designed on the basis of 100,000 creep-rupture strength, leaks were detected near the weld joints after only
22,000 h of operation. The objective of this study was to determine the cause of leakage in the pipe, which was made of grade
HP steel + Nb (Fe–33%Ni–20.5%Cr–1.4%Mn–1%Nb–1.05%Si–0.11%C) with an internal diameter of 254 mm and a wall thick-
818 Y.V. Nawancy, L.M. Al-Hadhrami / Engineering Failure Analysis 16 (2009) 816–824

Fig. 3. Secondary electron images illustrating intergranular cracks in the pipe near the weld as indicated by the arrows; (a) and (b) show the same area as
viewed at different magnifications.

Fig. 4. Secondary electron images illustrating voids at the weld–pipe interface as indicated by the arrows; same area viewed at different magnifications as
marked by 1 and 2.
 Y.V. Nawancy, L.M. Al-Hadhrami / Engineering Failure Analysis 16 (2009) 816–824 819

Fig. 5. Energy dispersive X-ray spectra illustrating the elements compositions of the pipe material (a) and weld (b), and the results of chemical analysis by
ICP-AES in comparison with the nominal compositions of the respective alloys.

ness of 24 mm. INCONLEL1 alloy 82 [(Ni + Co) not less than 67%–20%Cr–3%Fe–3%Mn–2.5%(Nb + Ta)–0.75%Ti–0.5%Si–0.5%Cu–
0.1%C] was used as a weld filler metal. Fig. 1b is a schematic illustrating the sample removed for analysis, which contained sec-
tions of the weld and pipe.

2. Experimental procedure

Representative metallographic samples were prepared from the as-received sample for microstructural characterization
and property evaluation. Scanning electron microscopy (SEM) combined with energy dispersive X-ray spectroscopy and ana-
lytical electron microscopy (AEM) were used to examine the microstructures. All AEM work was carried out at an acceler-
ating voltage of 200 KV. Thin foils for the transmission (TEM) and scanning transmission (STEM) electron microscopy modes
were prepared by the jet polishing technique. Inductively-coupled plasma-atomic energy spectroscopy (ICP-AES) was used
to measure the chemical compositions of the pipe material and filler metal. Microhardness measurements and stress-rupture
tests at 873 °C were used to evaluate the mechanical strength.

3. Results and discussion

3.1. Macroscopic features

A macrograph of the as-received section of the weld/pipe is shown in Fig. 2. In general, there was no evidence for mac-
roscopic cracks or distortion. Also, there was no indication that the pipe was subjected to high-temperature corrosion par-
ticularly carburization attack. However, cracks were detected on the microscopic scale particularly along grain boundaries of
the pipe material near the weld as shown below.

1
INCONLE is a registered trademark of the INCO family of companies.
820 Y.V. Nawancy, L.M. Al-Hadhrami / Engineering Failure Analysis 16 (2009) 816–824

3.2. Gross microscopic features

Fig. 3 shows secondary electron images illustrating gross microstructural features of the pipe material near the weld.
Intergranular cracks were detected in the pipe particularly in regions adjacent to the weld as shown in Fig. 3b. Also, microv-
oids were observed at the weld–pipe interface as shown in the example of Fig. 4. In contrast, no cracking could be detected in
regions far remove from the weld.
Energy dispersive X-ray spectra illustrating the elemental compositions of the pipe material and weld filler metal are
shown in Fig. 5. Also shown are the nominal compositions of both materials in comparison with the compositions measured
by ICP-AES. It is observed that the measured compositions are consistent with those of HP steel + Nb (pipe) and INCONEL
alloy 82 (filler metal) as specified.
Generally, steels used in reformer applications are selected on the basis of their 100,000 h creep strength and resistance to
carburization. It is known that the resistance to carburization increases by a factor of 3 as the ratio of (Ni/Fe + Cr) in weight %
is increased from 0.3 to 1 [4–7]. As shown in Fig. 5, the actual ratio for the pipe material is about 0.5 suggesting that max-
imum resistance to carburization was not a pre-requisite for the application consistent with the observation that the pipe
was not subjected to carburization attack. Therefore, the Si content of the steel grade selected for the application was unnec-
essarily high. As shown later, the problem was compounded by the simultaneous presence of Nb in both the pipe material
and filler metal. Both Si and Nb can have adverse effects on weldability [3].
Based upon the above observations, the leakage appeared to have occurred as a result of a localized phenomenon
near the weld leading to the formation of intergranular cracks in the pipe material. As shown later, this was corre-
lated with intergranular precipitation of Laves phase, which is known to degrade rupture ductility at elevated
temperatures.

3.3. Rupture strength of the pipe material

Since the ratio of internal diameter (d = 254 mm) to wall thickness (t = 24 mm) of the manifold pipe >10–15 (d/t = 10.58),
the stresses generated by the internal pressure P can be calculated on the basis of a thin-walled cylinder [8]. In this case,
the maximum principal stress (circumferential stress), which tends to produce longitudinal rupture is given by
r1 = Pd/2t = 10 MPa as schematically illustrated in Fig. 6a. A rough estimate of the 100,000 h rupture strength was obtained
by extrapolating short-term data as shown in Fig. 6b and found to be about 30 MPa. However, because of a slight bending of

Fig. 6. (a) A schematic illustrating the distribution of stresses generated in the pipe (thin-walled cylinder) by the internal pressure. (b) Stress rupture life of
HP steel + Nb at 873 °C extrapolated to 100,000 h.
 Y.V. Nawancy, L.M. Al-Hadhrami / Engineering Failure Analysis 16 (2009) 816–824 821

Fig. 7. An example illustrating the results of analyzing the intergranular precipitates in the pipe near the weld using scanning electron microscopy and
energy dispersive X-ray spectroscopy. (a) Backscattered electron image of the precipitates. (b) Elemental composition of the region marked 1 corresponding
to Laves phase. (c) Elemental composition of the region marked 2 corresponding to the Cr-rich M23C6 carbide. (d) Elemental composition of the region
marked 3 corresponding to the matrix phase.

the line representing rupture life after extended exposure, the actual rupture strength could be somewhat lower than 30 MP.
However, it highly unlikely, that the cracking was related to higher than normal operating pressure as further confirmed by
the detailed microstructural characterization described below.

3.4. Identification of secondary precipitates in the pipe material

Detailed microstructural characterization of the pipe material revealed the presence of massive intergranular precip-
itates near the weld as shown in the backscattered electron image of Fig. 7a. Microchemical analysis showed that the
major elemental constituents of most precipitates were Ni, Nb, and Si as shown in the energy dispersive X-ray spectrum
of Fig. 7b. Other precipitates present to a lesser extent were found to be enriched in Cr and C as shown in Fig. 7c. For
comparative purposes, Fig. 7d shows the elemental composition of the matrix phase. On the finer scale of transmission
electron microscopy, both electron diffraction and microchemical analysis showed that the Nb- and Si-rich precipitate
was a Laves phase of the type Ni3Nb2Si (hexagonal structure: a = 0.481 nm, c = 0.783 nm) as demonstrated in the exam-
ple of Fig. 8. Although most of the intergranular Laves phase assumed a lamellar morphology, it was also present in the
form of blocky particles. The Cr-rich precipitate was identified to be a carbide of the type M23C6 (face-centered cubic
structure: a = 1.76 nm) as illustrated in Fig. 9a. Typically, the characteristic reflections of this carbide appear at every
one-third position of the reflections corresponding to the matrix phase as shown in the h0 0 1i diffraction pattern of
Fig. 9b.
Although a binary Ni–Nb Laves phase is thermodynamically unstable, it can be stabilized by Si [9]. This could be related to
the effect of Si on the average electron concentration. It is known that Laves phases are unstable in binary systems with an
average electron concentration equal to or greater than 8 [9]. However, Si could have the effect of shifting the average elec-
tron concentration to a lower level stabilizing Laves phases as demonstrated in the present case. Therefore, most evidence
pointed out that the major factor contributing to the formation of Laves phase in the weld fusion zone was the relatively high
Si content of the pipe material and filler metal. Fig. 10 shows a backscattered electron image and corresponding X-ray map-
822 Y.V. Nawancy, L.M. Al-Hadhrami / Engineering Failure Analysis 16 (2009) 816–824

Fig. 8. An example illustrating the identification of intergranular precipitates of Laves phase by analytical electron microscopy. (a) Bright-field image of a
precipitate particle showing a high density of planar defects typical of Laves phase. (b) and (c) are electron diffraction patterns derived from the precipitate
 0 orientations respectively. (d) Energy dispersive X-ray spectrum derived from the precipitate in (a) and the results of
particle in [0 0 0 1] and ½0 1 1
quantifying the spectral data using the thin-film approximation.

Fig. 9. An example illustrating the identification of M23C6 carbide at a grain boundary. (a) Bright-field image showing an M23C6 carbide particle attached to
a particle of Laves phase. (b) h0 0 1i electron diffraction pattern derived from the carbide particle showing its characteristic reflections at every one-third
position of the reflections corresponding to the matrix phase (lattice constant of the carbide 3 times the lattice constant of the matrix phase).

ping image illustrating the preferential segregation of Si in the Laves phase near the weld. Precipitation of the secondary
M23C6 carbide could be related to partial decomposition of primary MC-type carbides with extended exposure at elevated
temperatures [10].
 Y.V. Nawancy, L.M. Al-Hadhrami / Engineering Failure Analysis 16 (2009) 816–824 823

Fig. 10. Typical distribution of Si near the weld. (a) Backscattered electron image showing the interfacial region between the weld and pipe. (b)
Corresponding X-ray mapping image of Si showing its preferential segregation to the Laves phase, which tends to assume a lamellar morphology.

Fig. 11. Secondary electron images of a cross-section of the pipe near the weld showing voids (a) and intergranular cracks (b) associated with the
precipitation of Laves phase.
824 Y.V. Nawancy, L.M. Al-Hadhrami / Engineering Failure Analysis 16 (2009) 816–824

Fig. 12. Comparative microhardness of intergranular Laves phase and the matrix phase near the weld.

3.5. Failure mode

Experimental results indicated that the mode of failure of the pipe was intergranular cracking in the vicinity of the weld.
These cracks were found to be associated with grain boundary precipitation of Laves phase as shown in the example of
Fig. 11. It is well known that this causes a loss of rupture ductility and associated cracking in weld fusion zones [9]. As ex-
pected, microhardness measurements showed that the grain boundaries of the pipe near the weld were embrittled by pre-
cipitation of Laves phase as illustrated in Fig. 12.

4. Conclusion

It is concluded from this study that the premature failure of the outlet manifold pipe in the weld fusion zone was caused
by selection of pipe material and weld filler metal with relatively high Si contents in the presence of Nb. This was found to
promote the intergranular precipitation of Ni3Nb2Si Laves phase in the weld fusion zone leading to localized loss of rupture
ductility and associated intergranular cracking.

Acknowledgement

It is a pleasure to acknowledge the continued support of King Fahd University of Petroleum and Minerals.

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