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4.2.1 Graphitization 4.2.1.1 Description of Damage

1) Graphitization is a change in the microstructure of certain carbon steels and 0.5Mo steels that occurs after long-term exposure to temperatures between 800-1100°F, causing a loss of strength, ductility, and creep resistance. 2) It occurs as the carbide phases in these steels decompose into graphite nodules over time at elevated temperatures. 3) It most commonly affects piping and equipment in fluid catalytic cracking, catalytic reforming, and coker units operating in this temperature range. The addition of chromium to the steel composition can prevent graphitization.

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238 views

4.2.1 Graphitization 4.2.1.1 Description of Damage

1) Graphitization is a change in the microstructure of certain carbon steels and 0.5Mo steels that occurs after long-term exposure to temperatures between 800-1100°F, causing a loss of strength, ductility, and creep resistance. 2) It occurs as the carbide phases in these steels decompose into graphite nodules over time at elevated temperatures. 3) It most commonly affects piping and equipment in fluid catalytic cracking, catalytic reforming, and coker units operating in this temperature range. The addition of chromium to the steel composition can prevent graphitization.

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Ajmi Hmida
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© © All Rights Reserved
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4.2.

1 Graphitization

4.2.1.1 Description of Damage


a) Graphitization is a change in the microstructure of certain carbon steels and 0.5Mo steels after long-
term operation in the 800°F to 1100°F (427°C to 593°C) range that may cause a loss in strength,
ductility, and/or creep resistance.
b) At elevated temperatures, the carbide phases in these steels are unstable and may decompose into
graphite nodules. This decomposition is known as graphitization.

4.2.1.2 Affected Materials


Some grades of carbon steel and 0.5Mo steels.

4.2.1.3 Critical Factors


a) The most important factors that affect graphitization are the chemistry, stress, temperature, and time
of exposure.
b) In general, graphitization is not commonly observed. Some steels are much more susceptible to
graphitization than others, but exactly what causes some steels to graphitize while others are
resistant is not well understood. It was originally thought that silicon and aluminum content played a
major role but it has been shown that they have negligible influence on graphitization.
c) Graphitization has been found in low alloy C-Mo steels with up to 1% Mo. The addition of about
0.7% chromium has been found to eliminate graphitization.
d) Temperature has an important effect on the rate of graphitization. Below 800°F (427°C), the rate is
extremely slow. The rate increases with increasing temperature.
e) There are two general types of graphitization. First is random graphitization in which the graphite
nodules are distributed randomly throughout the steel. While this type of graphitization may lower the
room-temperature tensile strength, it does not usually lower the creep resistance.
f) The second and more damaging type of graphitization results in chains or local planes of
concentrated graphite nodules. This form of graphitization can result in a significant reduction in load
bearing capability while increasing the potential for brittle fracture along this plane. The two forms of
this type of graphitization are weld heat-affected zone graphitization and non-weld graphitization.

1) Weld heat-affected zone graphitization is most frequently found in the heat-affected zone
adjacent to welds in a narrow band, corresponding to the low temperature edge of the heat-
affected zone. In multipass welded butt joints, these zones overlap each other, covering the
entire cross-section. Graphite nodules can form at the low temperature edge of these heat-
affected zones, resulting in a band of weak graphite extending across the section. Because of
its appearance, this graphite formation within heat-affected zones is called eyebrow
graphitization.
2) Non-weld graphitization is a form of localized graphitization that sometimes occurs along planes
of localized yielding in steel. It also occurs in a chain-like manner in regions that have
experienced significant plastic deformation as a result of cold working operations or bending.
g) The extent and degree of graphitization is usually reported in a qualitative fashion (none, slight,
moderate, severe). Although it is difficult to predict the rate at which it forms, severe heat-affected
zone graphitization can develop in as little as five years at service temperatures above 1000°F
(538°C). Very slight graphitization would be expected to be found after 30 to 40 years at 850°F
(454°C). Time-Temperature-Transformation curves for heat-affected zone graphitization can be
found in Reference 2.

4.2.1.4 Affected Units or Equipment


a) Primarily hot-wall piping and equipment in the FCC, catalytic reforming and coker units.
a) Bainitic grades are less susceptible than coarse pearlitic grades.
b) Few failures directly attributable to graphitization have been reported in the refining industry.
However, graphitization has been found where failure resulted primarily from other causes.
c) Several serious cases of graphitization have occurred in the reactors and piping of fluid catalytic
cracking units, as well as with carbon steel furnace tubes in a thermal cracking unit and the failure of
seal welds at the bottom tube sheet of a vertical waste heat boiler in a fluid catalytic cracker. A
graphitization failure was reported in the long seam weld of a C-0.5Mo catalytic reformer
reactor/interheater line.
d) Where concentrated eyebrow graphitization occurs along heat-affected zones, the creep rupture
strength may be drastically lowered. Slight to moderate amounts of graphite along the heat-affected
zones do not appear to significantly lower room or high-temperature properties.
e) Graphitization seldom occurs on boiling surface tubing but did occur in low alloy C-0.5Mo tubes and
headers during the 1940’s. Economizer tubing, steam piping and other equipment that operates in
the range of temperatures of 850°F to 1025°F (441°C to 552°C) is more likely to suffer graphitization.

4.2.1.5 Appearance or Morphology of Damage


a) Damage due to graphitization is not visible or readily apparent and can only be observed by
metallographic examination (Figure 4-1 and Figure 4-2).
b) Advanced stages of damage related to loss in creep strength may include microfissuring/microvoid
formation, subsurface cracking or surface connected cracking.

4.2.1.6 Prevention / Mitigation


Graphitization can be prevented by using chromium containing low alloy steels for long-term operation
above 800°F (427°C).

4.2.1.7 Inspection and Monitoring


a) Evidence of graphitization is most effectively evaluated through removal of full thickness samples for
examination using metallographic techniques. Damage may occur midwall so that field replicas may
be inadequate.
b) Advanced stages of damage related to loss in strength include surface breaking cracks or creep
deformation that may be difficult to detect.

4.2.1.8 Related Mechanisms


Spheroidization (see 4.2.2) and graphitization are competing mechanisms that occur at overlapping
temperature ranges. Spheroidization tends to occur preferentially above 1025°F (551°C), while
graphitization predominates below this temperature.

4.2.1.9 References
1. H. Thielsch, “Defects and Failures in Pressure Vessels and Piping,” Rheinhold Publishing Co., New
York, 1965, pp. 49-83.
2. J.R. Foulds and R. Viswanathan, “Graphitization of Steels in Elevated-Temperature Service,”
Proceedings of the First International Symposium: Microstructures and Mechanical Properties of
Aging Materials, November, 1992.
3. R.D. Port, “Non-Weld Related Graphitization Failures,” CORROSION/89, Paper #248, (Houston:
NACE 1989).
4. ASM Metals Handbook, “Properties and Selection: Iron, Steels, and High-Performance Alloys,”
Volume 1, ASM International, Materials Park, OH.
5. D.N. French, “Microstructural Degradation,” The National Board of Boiler and Pressure Vessel
Inspectors, http://www.nationalboard.com, June 2001.
6. Joseph G. Wilson, “Graphitization of Steel in Petroleum Refining Equipment and the Effect of
Graphitization of Steel on Stress-Rupture Properties,” WRC Bulletin Series, No.32, Shaker Heights,
OH, January, 1957.
7. J. D Dobis and L. Huang, “Assessment of Graphitized Carbon Steel Tubes in Fired Heater Service,”
CORROSION/05, NACE International, paper #05559, Houston, TX, 2005.
Figure 4-1 – High magnification photomicrograph of metallographic sample showing graphite
nodules. Compare to normal microstructure shown in Figure 4-2.

Figure 4-2 – High magnification photomicrograph of metallographic sample showing typical


ferrite-pearlite structure of carbon steel.

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