Materials Technology, Vol. 20, Issue 3, pp. 141-145, 2005.

Intergranular Embrittlement of SS 321 alloy due to

High Temperature Carburization

Anwar Ul-Hamid∗, Hani M. Tawancy, Nureddin M. Abbas

Center for Engineering Research, Research Institute, King Fahd University of Petroleum &
Minerals, P. O. Box 1073, Dhahran 31261, Saudi Arabia.

Abstract
An outlet header flange of a furnace used to preheat isobutane from about 180°C to 635°C
developed cracks after about 5 years of operation. A hot-rolled plate of type 321 stainless steel
(UNS S32100) was used to manufacture the flange, which was welded to a T-joint. Scanning
electron microscopy (SEM) and microchemical analysis by energy dispersive X-ray spectroscopy
(EDS) were used to characterize the microstructure of the failed flange section. Microhardness
measurements were used to evaluate the mechanical strength. Experimental results showed that
the mode of failure was high temperature carburization attack leading to intergranular
embrittlement. It was recommended as an immediate measure to identify means for preventing
partial cracking of isobutane during heating which resulted in carburization. However, if this
proved to be impractical, it was recommended to consider replacing the material with a more
carburization resistant alloy.

Introduction
Isobutane was cracked in a downstream reactor. Prior to cracking, the temperature of isobutane
was raised from 180-200 °C to 630-635°C in a furnace by means of a heating coil. Although,
every effort was made to avoid isobutane cracking at the preheating stage, some cracking did
occur at an operating pressure that ranged from 0.97-1.2 Kg/cm2. Preheated isobutane was
transported from the furnace using an insulated pipe containing a flange welded to a T-joint at the
outlet. Both the flange and T-joint were made of type 321 stainless steel plates. The thickness of
the plate used to manufacture the flange was 15.1 mm and that of the T-joint was 22 mm.
The composition (in weight %) of the process fluid was: 96.97% isobutane, 0.68% propane,
0.51% isobutylene, 0.50% normal butane, 0.43% T-2 butane, 0.33% C-2 butane, 0.32% I-butane,
0.15% propylene, 0.09% 1,3 butadiene, and 0.02% methane.
The furnace gave satisfactory performance for 5 years into service. After this period, leakage
was observed at the flange. Removal of insulating material revealed cracks between the flange
and T-joint in the weld heat affected zone.

Experimental Procedure
Selected samples were removed from the failed section of the flange. Microchemical analysis
by conventional energy dispersive X-ray spectroscopy (EDS) in a scanning electron microscope
(SEM) was used for material verification. Both the secondary and backscattered modes of SEM
were used to characterize the grain structure. To reveal the grain structure, specimens were
etched in a nital+chromic acid solution. Microhardness measurements were used to evaluate the
mechanical strength.

Results and Discussion

Visual Inspection

∗
Corresponding author: Tel.: +966-3-860-2017, Fax: +966-3-860-4442, email: anwar@kfupm.edu.sa

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 A photograph illustrating the general appearance of the as-received section of the flange is
shown in figure 1. Cracks near the weld can be seen as indicated by the arrows. It can be noted
that the cracks followed a zigzag path suggesting that they occurred at grain boundaries. The
cracks were initiated at the inner surface signifying a process irregularity. Also, the inner surface
of the flange contained a black layer typical of a coke deposit.
The above observations suggested that the failed component was subject to high-temperature
carburization attack. It is known that carburization degrades the mechanical strength of structural
alloys, which could lead to severe embrittlement [1-3]. Metallurgical evaluation confirmed the
above suggestion as described later.

Material Verification
An energy dispersive X-ray spectrum representative of the flange material is shown in figure 2.
Table 1 summarizes the results of quantifying the spectral data in comparison with the nominal
composition of type 321 stainless steel. The observed composition was found to be in agreement
with the nominal composition confirming that the material of the flange was SS 321 steel. Type
321 stainless steel is known for its stability toward carbide precipitation due to its Ti content [4].
Its recommended uses include welded equipment exposed to corrosive environments, which
could operate at temperatures in the sensitization range (425-900 °C), i.e. temperatures at which
grain boundary precipitation of carbide phases could occur. Previous studies of the carburization
resistance of Fe-Cr-Ni austenitic stainless steels, where Cr and Fe are the major carbide-forming
elements, show that their resistance to carburization is considerably degraded as the (Ni/(Fe+Cr))
ratio is decreased to below about 0.3 [1,5]. Reference to Table 2 shows that the (Ni/(Fe+Cr)) ratio
of 321 stainless steel is about 0.1 indicating that this type of steel is not considered to be resistant
to high temperature carburization.
Grain Structure
Figure 3 illustrates the gross grain structure of the weld and flange material. Elongation of the
grains near the weld regions was observed indicating that the material was cold worked. Other
microstructural features of the flange material are illustrated in the secondary and backscattered
electron SEM images of figure 4a and b. Stringers of small particles can be seen as indicated by
the arrows marked A. These particles were found to be Ti-rich suggesting that they were of a
primary MC-type carbide as expected in type 321 stainless steel. Also, fine striations typical of
slip lines are observed within some of the grains as indicated by the arrows marked B. However,
near the weld region and away from the cracks, a considerable increase in the density of slip lines
occurred, and the grains became coarser as can be seen by comparing figures 4 and 5. If
compared with the grain size of annealed SS 321 steel [6], it appeared that the material was
subjected to localized grain growth degrading its tensile strength.
Based upon the above observations, it could be concluded that the flange material was subject
to high levels of stress in localized regions. Also, the results suggested the possibility of localized
overheating leading to a considerable grain growth. It is noted that both the localized high stress
level and overheating could result from high-temperature carburization attack [7] as further
described later
Mode of Fracture
An example illustrating the analysis of fracture surface is given in figure 6. In the as-received
condition, the surface contained a relatively thick layer of deposit as shown in figure 6a. As can
be seen from the energy dispersive X-ray spectrum of figure 6b, the deposit was Cr-rich and

14 2
contained a marked concentration of Fe in addition to a trace amount of Ni as expected of a
carbide phase [2]. It is to be noted that C could not be detected by the EDS detector used for the
analysis. Figure 7 demonstrates the intergranular nature of the cracks. A precipitate layer of
carbide similar to that shown in figure 6 can be seen to delineate the grain boundaries. A low-
magnification image illustrating the extent of carburization is shown in figure 8. As can be seen,
the thickness of the carburized layer in this region ranged from about 7 mm to 10 mm. After
removal some of the deposit on the fracture surface by polishing, the intergranular mode became
more evident as shown in the example of figure 9.
Evaluation of Mechanical Strength
Typically, in the annealed condition, the hardness of type 321 stainless steel is in the order of
Rb 80 corresponding to Vickers microhardness number (HV) of 160 [4]. Microhardness
measurements across a carburized layer and into the base metal as shown in figure 8 showed that
the average hardness near the surface was about HV 250. It then decreased with depth until it
approached the value typical of the base metal. These results demonstrated the considerable
hardening effect produced by carburization.
Mode of Failure
Based upon the experimental results, it could be concluded that the mode of failure was
intergranular embrittlement of SS 321 type alloy due to high-temperature carburization. It is well
known that carburization has detrimental effects on the mechanical strength of alloys [1-3].
Firstly, high levels of stresses are generated in carburized and uncarburized regions due to the
differences in their thermal expansion characteristics. Secondly, a higher tube wall temperature is
required to maintain the same fluid temperature due to insulating effect of the deposited coke.
This accelerates the rate of carburization and causes a considerable localized grain growth as
observed in this study.
Cause of Failure
It was evident that carbon was continuously generated during the heating process from
carbonaceous gases such as hydrocarbons, e.g. methane, resulting from partial cracking of
isobutane. Consequently, a large amount of coke was deposited at the material surface. Type 321
stainless steel does not have an adequate resistance to high-temperature carburization in view of
its relatively high (Fe+Cr) content and low Ni content. Provided that carburization was
anticipated as a service condition, the cause of failure would be improper selection of material.
However, if it was thought that no cracking of isobutane would occur under the specified
operating conditions, the cause of failure can be termed as unanticipated service conditions.

Recommendations
In view of the above results, it was recommended as an immediate measure to consider means
for preventing partial cracking of isobutane. However, if this proved to be impractical,
replacement of type 321 stainless steel with one of the materials adequately resistant to high-
temperature carburization was suggested. Examples of such alloys include Fe-base alloy 800H
(UNS N08810) or type 314 stainless steel (UNS S31400). However, the materials most resistant
to carburization attack are those capable of developing Al2O3 protective scale such as the Ni-base
HAYNES alloy No. 214 (UNS N07214).

Acknowledgements
The authors wish to acknowledge the support of the Research Institute of King Fahd University

143
of Petroleum & Minerals, Dhahran, Saudi Arabia.

References

[1] H.M. Tawancy, "Structure and Properties of High Temperature Alloys: Applications of
Analytical Electron Microscopy", KFUPM press, Dhahran, 1993,pp. 288.
[2] H.M. Tawancy and N. M. Abbas, Journal of Materials Science, Vol. 27, 1992, pp. 106.
[3] G.Y. Lai, High-Temperature Corrosion of Engineering Alloys, ASM International, Materials
Park, Ohio, 1990, pp. 47.
[4] J.C. Bittence (editor), Materials Engineering: 1983 Materials Selector, Penton Publishing
Company, Cleveland, Ohio, December 1982, pp. C36.
[5] J.F. Norton, L. Blidegen, S. Canetoli, and P.D. Frampton, Werksoffe und Korrosion, vol. 32,
1982, pp. 467.
[6] Metals Handbook: Atlas of Microstructures of Industrial Alloys, vol. 7, eighth edition, ASM,
Metals Park, Ohio, 1973, pp. 140.
[7] J. Norton, Carburization in High-Temperature Process Plant Materials, Commission of the
European Communities, Petten Establishment, Holland, Report No. EUR 7773, 1981, pp. 7 and
pp. 44.

FIGURE CAPTIONS

Figure 1 - Photographs illustrating the general appearance of the as-received section of the
flange; cracks near the weld are indicated by the arrows

Figure 2 – EDS spectrum representative of the flange material.

Figure 3 - A secondary electron SEM image illustrating the gross grain structure of the weld and
flange; elongation of the grains near the weld is indicative of cold work.

Figure 4 – (a) Secondary and (b) backscattered SEM images showing stringers of Ti-rich carbide
(A) and fine striations corresponding to slip lines (B).

Figure 5 - SEM image illustrating slip lines within grains of the flange material near the weld
region.

Figure 6 – (a) SEM image showing fracture surface with a thick deposit, (b) EDS spectrum from
the encircled region in (a) indicating that the deposit was Cr-rich.

Figure 7 - SEM image illustrating intergranular cracks in the flange material as indicated by the
arrows. Grain boundaries are delineated with a precipitate layer of carbide.

Figure 8 - A low-magnification composite image illustrating the granular appearance of the

fracture surface typifying an intergranular fracture mode; the thickness of the carburized layer
ranged from 7 mm to 10 mm.

Figure 9 - SEM image of the fracture surface after polishing; some of the deposit was removed to
illustrate the intergranular mode of fracture.

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Table 1. Nominal and measured chemical composition (weight %) of type 321 stainless steel

Element Chemical composition (weight %)

Nominal Measured
Fe Balance 72.39
Cr 17-19 17.54
Ni 9-12 9.05
Mn 2* ND
*
Si 1 0.36
C 0.08* ND
**
Ti 5XC 0.67
*
Maximum
**
Minimum
ND ≡ Nor Detected

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Figure 1
Figure 2
Figure 3
Figure 4a
Figure 4b
Figure 5
Figure 6a
Figure 6b
Figure 7
Figure 8
Figure 9