Copyrighted material licensed to Saudi Aramco. No further reproduction or distribution permitted.

Printed / viewed by: [rabdad.khan@aramco.com] @ 2012-07-31

Damage Mechanisms Affecting Fixed Equipment in the Refining Industry 4-147
_____________________________________________________________________________________________

4.3.12 Graphitic Corrosion

4.3.12.1 Description of Damage

a) Cast irons are comprised of graphite particles embedded in an iron matrix. Graphitic corrosion is a
form of dealloying in which the iron matrix is corroded, leaving corrosion products and porous
graphite.
b) Attack results in a porous structure with a loss of strength, ductility and density. It usually occurs
under low pH and stagnant conditions, especially in contact with soils or waters high in sulfates.

4.3.12.2 Affected Materials

Primarily gray cast iron, but also nodular and malleable cast irons experience graphitic corrosion.
However, nodular and malleable cast irons tend to crumble when attacked. White iron is not subject to
this damage because there is no free graphite.

4.3.12.3 Critical Factors

a) Graphitic corrosion occurs with several different cast iron alloys but is usually limited to very specific
microstructure-environment combinations. Factors that influence graphitic corrosion include the
composition of the alloy and exposure conditions including temperature, degree of aeration, pH and
exposure time.
b) Damage occurs in the presence of moisture or an aqueous phase, usually below 200°F (93°C).
c) Damage may take many months or years to progress but can increase in severity if the pH drops.
Much of the damage occurs during stagnant conditions when high concentrations of sulfates are
present.
d) Graphite is cathodic to the iron matrix. The iron matrix preferentially corrodes and cathodically
protects the graphite in certain conductive waters or soils.
e) Graphitic corrosion may affect adjacent components by causing galvanic corrosion.

4.3.12.4 Affected Units or Equipment

Graphitic corrosion can occur in soft water, salt water, mine waters, dilute acids and in underground
piping as well as in boiler feedwater equipment. Typical examples include feedwater piping, pumps
(including pump impellers), valves, and underground cast iron pipe. Fire water systems are particularly
vulnerable.

4.3.12.5 Appearance or Morphology of Damage

a) Damage may be widespread or it may also occur in localized areas in which the majority of the
component is unaffected.
b) The damage may not be noticeable upon visual inspection even where the full wall thickness is
degraded.
c) Damaged areas will be soft and easily gouged with a knife or hand tool.
d) Metallographic examination may be required to confirm the extent of damage (Figure 4-103 through
Figure 4-110).

4.3.12.6 Inspection and Monitoring

a) UT is not a good method for detecting damage.
b) Acoustic techniques (loss of “metallic ring”) and ultrasonic attenuation are applicable.
c) A significant reduction in hardness may accompany dealloying, although affected areas may be
localized.
 Copyrighted material licensed to Saudi Aramco. No further reproduction or distribution permitted.
Printed / viewed by: [rabdad.khan@aramco.com] @ 2012-07-31
4-148 API Recommended Practice 571
_____________________________________________________________________________________________

4.3.12.7 Prevention / Mitigation

a) It is often difficult to predict if exposure conditions will cause this form of dealloying in a particular
environment or service. One must be aware of the potential susceptibility of cast irons.
b) Internal graphitic corrosion can be prevented by coatings and/or cement linings.
c) External graphitic corrosion can be prevented by external coatings or cathodic protection in severely
corrosive soils.

4.3.12.8 Related Mechanisms

Also known as selective leaching, graphitic corrosion is a form of dealloying (see 4.3.11) of cast irons. It
should not be confused with graphitization, the decomposition of carbides at high temperatures (see
4.2.1).

4.3.12.9 References
1. R.D. Port and H.M. Herro, “The NALCO Guide to Boiler Failure Analysis,” McGraw-Hill, Inc., NY,
1991, pp. 259-263.
2. ASM Metals Handbook, “Failure Analysis and Prevention,” Volume 11, ASM International, Materials
Park, OH.
3. ASM Metals Handbook, “Corrosion,” Volume 13, ASM International, Materials Park, OH.
 Copyrighted material licensed to Saudi Aramco. No further reproduction or distribution permitted.
Printed / viewed by: [rabdad.khan@aramco.com] @ 2012-07-31
Damage Mechanisms Affecting Fixed Equipment in the Refining Industry 4-149
_____________________________________________________________________________________________

Figure 4-103 – Graphitic Corrosion of cast iron impeller due to glycol acidification.

Figure 4-104 – Cut away of cast iron impeller shown above. The dark phase around the outside
perimeter (at arrows) is graphite which surround the unaffected metal in the middle.
 Copyrighted material licensed to Saudi Aramco. No further reproduction or distribution permitted.
Printed / viewed by: [rabdad.khan@aramco.com] @ 2012-07-31
4-150 API Recommended Practice 571
_____________________________________________________________________________________________

Figure 4-105 – View of the outside of an underground concrete-lined salt water service line that
failed from graphitic corrosion.

Figure 4-106 – View of concrete lining inside the failed line shown in Figure 105.
 Copyrighted material licensed to Saudi Aramco. No further reproduction or distribution permitted.
Printed / viewed by: [rabdad.khan@aramco.com] @ 2012-07-31
Damage Mechanisms Affecting Fixed Equipment in the Refining Industry 4-151
_____________________________________________________________________________________________

Figure 4-107 – Cross section of a gray cast iron drainpipe showing charcoal colored thru-wall
graphitic corrosion encroaching from both sides. Note the through wall crack at the bottom.

Figure 4-108 – Cross section of a gray cast iron pipe with graphitic corrosion coming from O.D.
(Point B).
 Copyrighted material licensed to Saudi Aramco. No further reproduction or distribution permitted.
Printed / viewed by: [rabdad.khan@aramco.com] @ 2012-07-31
4-152 API Recommended Practice 571
_____________________________________________________________________________________________

Figure 4-109 – Higher magnification view of unaffected area “A” shown in Figure 4-108.

Figure 4-110 – Higher magnification view of the damage from shown in 4-108 (area “B”).
 Copyrighted material licensed to Saudi Aramco. No further reproduction or distribution permitted.
Printed / viewed by: [rabdad.khan@aramco.com] @ 2012-07-31
Damage Mechanisms Affecting Fixed Equipment in the Refining Industry 4-153
_____________________________________________________________________________________________

4.4 High Temperature Corrosion [>400°F (204°C)]

4.4.1 Oxidation

4.4.1.1 Description of Damage

a) Oxygen reacts with carbon steel and other alloys at high temperature converting the metal to oxide
scale.
b) It is most often present as oxygen is in the surrounding air (approximately 20%) used for combustion
in fired heaters and boilers.

4.4.1.2 Affected Materials

a) All iron based materials including carbon steel and low alloy steels, both cast and wrought.
b) All 300 Series SS, 400 Series SS and nickel base alloys also oxidize to varying degrees, depending
on composition and temperature.

4.4.1.3 Critical Factors

a) The primary factors affecting high temperature oxidation are metal temperature and alloy
composition.
b) Oxidation of carbon steel begins to become significant above about 1000°F (538°C). Rates of metal
loss increase with increasing temperature.
c) In general, the resistance of carbon steel and other alloys is determined by the chromium content of
the material. Increasing chromium levels produce a more protective oxide scale. The 300 Series SS
are resistant to scaling up to about 1500°F (816°C). See Table 4-8.
d) The presence of water vapor can significantly accelerate oxidation rates of some steels including
9Cr-1Mo (Reference 4.)

4.4.1.4 Affected Units or Equipment

Oxidation occurs in fired heaters and boilers as well as other combustion equipment, piping and
equipment that operates in high temperature environments when metal temperatures exceed about
1000°F (538°C).

4.4.1.5 Appearance or Morphology of Damage

a) Most alloys, including carbon steels and low alloy steels, suffer general thinning due to oxidation.
Usually, the component will be covered on the outside surface with an oxide scale, depending on the
temperature and exposure time (Figure 4-111 to 4-113).
b) 300 Series SS and nickel alloys generally have a very thin dark scale unless exposed to extremely
high temperatures where metal loss rates are excessive.

4.4.1.6 Prevention / Mitigation

a) Resistance to oxidation is best achieved by upgrading to a more resistant alloy.
b) Chromium is the primary alloying element that affects resistance to oxidation. Other alloying
elements, including silicon and aluminum, are effective but their concentrations are limited due to
adverse affects on mechanical properties. They are often used in special alloys for applications such
as heater supports, burner tips and components for combustion equipment.

4.4.1.7 Inspection and Monitoring

a) Process conditions should be monitored for establishing trends of high temperature equipment
where oxidation can occur.
 Copyrighted material licensed to Saudi Aramco. No further reproduction or distribution permitted.
Printed / viewed by: [rabdad.khan@aramco.com] @ 2012-07-31
4-154 API Recommended Practice 571
_____________________________________________________________________________________________

b) Temperatures can be monitored through the use of tubeskin thermocouples and/or infrared
thermography.
c) Loss in thickness due to oxidation is usually measured using external ultrasonic thickness
measurements.

4.4.1.8 Related Mechanisms

Oxidation damage referred to in this section is due to surface scaling. Some damage mechanisms result
in internal oxidation which is outside the scope of this document.

4.4.1.9 References
1. API RP 581, Risk-Based Inspection Technology, American Petroleum Institute, Washington, D.C.,
2008.
2. J. Gutzeit et al., “Corrosion in Petroleum Refining and Petrochemical Operations” ASM Metals
Handbook, Volume 13, ASM International, OH, 1987, pp. 1262 – 1288.
3. “Corrosion Basics – An Introduction,” NACE International, Houston, TX, 1984, pp. 276 - 288.
4. F. Dettenwanger et al., “The influence of Si, W and water vapor on the oxidation behavior of 9Cr
steels”, Paper No. 01151, NACE International, Houston, TX, 2001.