Damage Mechanisms Affecting Fixed

Equipment in the Refining Industry

 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 39

3.8 Atmospheric Corrosion

3.8.1 Description of Damage

Corrosion that occurs from moisture associated with atmospheric conditions. Marine environments and moist,
polluted industrial environments with airborne contaminants are the most severe. Dry rural environments cause
very little corrosion.

3.8.2 Affected Materials

Carbon steel, low-alloy steels, and copper alloyed aluminum.

3.8.3 Critical Factors

a) The physical location of the plant (industrial, marine, urban, rural).

b) The amount of moisture (humidity, rainfall) typically present or the presence of cooling tower mist.

c) The presence of salts, sulfur compounds, dirt, or other contaminants in the air.

d) Chlorides, H2S, fly ash, and other airborne contaminants from cooling tower and wet gas scrubber drift,
furnace stacks, and other equipment accelerate corrosion.

e) Orientation to the prevailing wind and rain.

f) Corrosion rates increase with temperature up to about 250 °F (120 °C). Above 250 °F (120 °C), surfaces are
usually too dry for corrosion to occur except under insulation. (See 3.22.)

g) Designs that trap water or moisture in crevices or other configurations are more prone to attack.

h) Marine environments can be very corrosive (about 20 mpy) as are industrial environments that contain acids
or sulfur compounds that can form acids (about 5 mpy to 10 mpy).

i) Inland locations exposed to a moderate amount of precipitation or humidity are considered moderately
corrosive environments (about 1 mpy to 3 mpy).

j) Dry rural environments usually have very low corrosion rates (<1 mpy).

k) Bird droppings can also cause accelerated corrosion and unsightly stains.

3.8.4 Affected Units or Equipment

a) Unpainted, uninsulated carbon steel and low-alloy steel piping and equipment operating below 250 °F
(120 °C) where moisture can contact the surface.

b) Uninsulated carbon and low-alloy steel equipment with deteriorated paint/coating.

c) Equipment downwind of cooling towers and wet gas scrubbers.

d) Equipment may be susceptible if cycled between ambient and higher or lower operating temperatures.

e) Equipment shut down or idled for prolonged periods unless properly mothballed.

f) Tanks and piping are particularly susceptible. Piping that rests on pipe supports is very prone to attack due
to water entrapment between the pipe and the support.

g) Piers and docks are very prone to attack from the marine environment.
40 API RECOMMENDED PRACTICE 571

h) Bimetallic connections such as copper to aluminum electrical connections.

3.8.5 Appearance or Morphology of Damage

a) The attack will be general or localized, depending upon the condition of the coating, if any, and whether or
not the moisture is trapped.

b) If there is no coating, corrosion or loss in thickness can be more general and widespread.

c) Localized coating failures will promote localized corrosion.

d) Metal loss may not be visually evident, although normally a distinctive iron oxide (red rust) scale forms as
shown in Figure 3-8-1.

3.8.6 Prevention/Mitigation

Paints or coatings are normally applied to otherwise unprotected equipment to prevent atmospheric corrosion.
Surface preparation and proper coating application are critical for long-term protection in corrosive environments.

3.8.7 Inspection and Monitoring

a) VT includes direct/line-of-sight and indirect methods using a camera, mirror, laser scanning, and/or structured
white light imaging with pit gages.

b) UT can include techniques like straight beam or angle beam (SWUT or PAUT) to directly measure remaining
wall thickness or screening techniques using EMAT or GWT.

c) RT may include traditional (film based), digital, or computed radiography media and may incorporate
techniques such as contact or profile RT as well as open system imaging.

d) ECT may include a screening technique such as pulsed eddy current (PEC).

3.8.8 Related Mechanisms

Corrosion under insulation (CUI) (3.22) and concentration cell (touch point) corrosion (3.19).
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 41

Figure 3-8-1—Atmospheric corrosion of an LPG line in close proximity to a cooling tower.

 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 49

3.11 Brittle Fracture

3.11.1 Description of Damage

Brittle fracture is the sudden rapid fracture under stress (residual or applied) where the material exhibits little or
no evidence of ductility or plastic deformation. Although rare in refining operations, in-service brittle fracture of a
pressure vessel or other pressurized equipment can have serious consequences.

3.11.2 Affected Materials

Carbon steels and low-alloy steels are of prime concern, particularly older steels. 400 series SS are also
susceptible even if not embrittled. In addition, materials susceptible to an embrittling mechanism such as sigma
phase embrittlement (3.56), 885 °F (475 °C) embrittlement (3.1), temper embrittlement (3.63), strain-aging
embrittlement (3.60), or titanium hydriding (3.66) pose a risk for brittle fracture if they are sufficiently embrittled.
The critical of factors in brittle fracture can occur ________.
3.11.3 Critical Factors Answer: the stress concentration effect of a flaw.

a) Brittle fracture can occur in a potentially susceptible piece of equipment containing a flaw or other significant
stress concentrator. Three primary factors are:

the material’s fracture toughness (resistance to crack-like flaws) as indicated in a Charpy impact test or
other fracture mechanics test;

the size, shape, and stress concentration effect of the flaw; and

the amount of residual and applied stresses on the flaw.

b) Susceptibility of a material to brittle fracture may be increased by the presence of embrittling phases.

c) Steel cleanliness (level of S, P, and other impurity elements) and grain size have a significant influence on
toughness and resistance to brittle fracture. In addition, higher-strength, micro-alloyed steels can experience
secondary hardening in certain temperature ranges due to the precipitation of embrittling phases that reduce
the fracture toughness of the steel. Micro-alloying elements like V, Cb (Nb), B, and Ti in certain ranges as
well as S, P, and Mn above their residual limits can cause low toughness.

d) The heat treatment condition of the material can affect its fracture toughness.

e) Thicker material sections have an inherently lower resistance to brittle fracture due to the nature of the stress
state within a thick section of metal. Thick sections are under higher constraint (i.e. they are constrained from
deforming), which increases triaxial stresses at the crack tip and promotes brittle, rather than ductile, fracture.

f) In most cases, in materials that exhibit a ductile-to-brittle transition, brittle fracture occurs only at temperatures
below the Charpy impact transition temperature (also called the ductile-to-brittle transition temperature), the
temperature at and below which the toughness of the material drops off sharply.

3.11.4 Affected Units or Equipment

a) Equipment manufactured to the ASME Boiler and Pressure Vessel Code (BPVC) Section VIII, Division 1,
prior to the December 1987 Addenda, had no Code-required restrictions on notch toughness for vessels
operating at cold temperatures. However, this does not mean that all vessels fabricated prior to this date will
be subject to brittle fracture. Many designers, purchasers, and users specified supplemental impact tests on
equipment that was intended to be in cold service.

Equipment made to the same code after this date were subject to the requirements of UCS 66 (impact
exemption curves), which address impact toughness requirements at low temperatures.

b) Most processes run at elevated temperature, so the main concern is for brittle fracture during start-up,
shutdown, or hydrotest/tightness testing. Thick wall equipment in particular in any unit should be evaluated.
50 API RECOMMENDED PRACTICE 571

c) Brittle fracture resulting from an autorefrigeration event should be considered in units processing light
hydrocarbons such as methane (CH4), ethane/ethylene, propane/propylene, or butane. This includes
alkylation units, olefin units, and polymer plants (polyethylene and polypropylene). Storage bullets and
spheres for light hydrocarbons may also be susceptible.

d) Brittle fracture can occur during ambient temperature hydrotesting due to high stresses and low toughness
at the testing temperature.

3.11.5 Appearance or Morphology of Damage

a) Cracks will typically be straight, non-branching, and largely devoid of any associated plastic deformation,
although fine shear lips may be found along the free edge of the fracture, or localized necking around the
crack may occur. (Figure 3-11-1 to Figure 3-11-5)

b) The fracture surface, if undamaged after the initial fracture, will exhibit visible “chevron markings” that point
back to the crack origin point. These markings can be helpful in locating the initiating cause of the brittle
fracture. (Figure 3-11-6)

c) Microscopically, the fracture surface will be composed largely of cleavage, with limited intergranular cracking
and very little microvoid coalescence.

3.11.6 Prevention/Mitigation

a) For most new equipment, brittle fracture is prevented by using materials compliant with UCS 66 in Section
VIII of the ASME BPVC. In some cases, equipment will need to be specifically designed for low-temperature
operation including upset and autorefrigeration events or will have additional requirements to account for a
large wall thickness. Materials with controlled chemical composition, special heat treatment, and/or impact
test verification may be required.

Using fully killed, fine grain steel with austenite grain size finer than 6 (McQuaid Ehn Method) will achieve
the desired toughness in many situations.

b) For existing equipment, the combination of stress, material toughness, and existing or potential flaw size
govern the probability of a brittle fracture event. In cases where there is a concern for the possibility of a brittle
fracture occurring, an engineering evaluation can be performed in accordance with API 579-1/ASME FFS-1,
Section 3, Level 1 or 2.

c) Preventing and minimizing the possibility of a brittle fracture in existing equipment rely upon controlling the
operating conditions (pressure, temperature), minimizing pressure at ambient temperatures during start-
up and shutdown, not hydrotesting at too low a temperature, and periodic inspection at high-stress
locations, as applicable to the specific situation. A pressure vessel can also be re-rated to a lower
maximum allowable working pressure (MAWP) and resulting new, higher minimum design metal
temperature (MDMT), per the requirements of the National Board Inspection Code, ASME BPVC Section
VIII, Division 1, or other jurisdictional requirements or codes.

d) Where brittle fracture is deemed a concern, some reduction in the likelihood of a brittle fracture may be
achieved by following API 579-1/ASME FFS-1.

e) In some cases, selecting or changing to a material with good low-temperature toughness, e.g. an appropriate
low-temperature ASTM/ASME grade of steel (often containing a few percent of nickel) or an austenitic (300
series) stainless steel, will be necessary to achieve the desired low-temperature fracture toughness.

3.11.7 Inspection and Monitoring

a) Routine inspection is not normally used to detect or mitigate brittle fracture, but awareness of susceptible
equipment can help prevent future damage.
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 51

b) Susceptible vessels can be inspected for pre-existing crack-like fabrication flaws, as well as for cracking from
relevant in-service cracking mechanisms using magnetic particle testing (MT), PT, and/or UT, as applicable.

3.11.8 Related Mechanisms

Temper embrittlement (3.63), strain age embrittlement (3.60), 885 °F (475 °C) embrittlement (3.1), titanium
hydriding (3.66), and sigma embrittlement (3.56).

3.11.9 References

1. API 579-1/ASME FFS-1, Fitness-For-Service, American Petroleum Institute, Washington, DC.

2. J.A. Smith and S.T. Rolfe, Part 1: Constraint Effects on Fracture Behavior: The Effect of Crack Depth (a) and
Crack-depth to Width Ratio (a/W) on the Fracture Toughness of A533-B Steel, WRC Bulletin 418, Welding
Research Council, Shaker Heights, OH.

3. British Standard 7910, Guide to Methods for Assessing the Acceptability of Flaws in Metallic Structures,
British Standards Institution, London, UK.

4. ASME Boiler and Pressure Vessel Code (BPVC), Section III: Rules for Constructions of Nuclear Facility
Components; Division 1, American Society of Mechanical Engineers, New York, NY.

Figure 3-11-1—20-in. carbon steel pipeline that failed during hydrotest at gouges on the OD.
52 API RECOMMENDED PRACTICE 571

Figure 3-11-2—Close-up of Figure 3-11-1 showing the gouges and

the fracture origin (arrow) in one of the gouges.

Figure 3-11-3—Brittle fracture of a 2.2-in. wall C-0.5Mo exchanger channel during hydrotest.
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 53

Figure 3-11-4—Brittle fracture of vessel shell during hydrotest.

Figure 3-11-5—Classic example of brittle fracture that occurred during hydrotest.

54 API RECOMMENDED PRACTICE 571

Figure 3-11-6—Close-up view of the fracture surface from a vessel made of A516-70N plate showing
the chevron pattern that points back toward the origin of the crack.
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 69

3.14 Caustic Corrosion

3.14.1 Description of Damage

Localized corrosion due to the concentration of caustic (alkaline) solutions such as NaOH and KOH, and/or
corrosive salts from those solutions, that usually occurs under evaporative or high heat transfer conditions
(commonly called caustic gouging). Also, corrosion resulting in general thinning can occur at elevated
temperatures, depending on alkali or caustic solution strength.

3.14.2 Affected Materials

Primarily carbon steel, low-alloy steels, and 400 series SS. Carbon steel is the material most commonly used in
situations where caustic corrosion is a concern. 300 series SS is generally resistant to caustic corrosion until
passivity is damaged, which can occur in the approximate temperature range of 160 °F to 210 °F (70 °C to
100 °C), depending on the concentration. 300 series SS can also be susceptible to caustic SCC at these elevated
temperatures. (See 3.15.)

3.14.3 Critical Factors

a) Caustic (NaOH or KOH) must be present. The following are sources of caustic.

Caustic is commonly added to treat BFW and may also enter inadvertently during regeneration of
demineralizers.

Caustic is sometimes added to process streams for acid neutralization or as a reactant to remove sulfur
or chlorides.

Alkaline solutions or salts may also enter process streams through leaks in condensers or other process
equipment.

Concentrated caustic is handled in the storage and feed equipment used for feeding caustic into BFW
or process streams.

b) In high-solution-strength caustic, temperatures above about 170 °F (75 °C), with the temperature limit
depending on the caustic concentration, will cause general corrosion of carbon steel. (See Figure 3-15-1 in
3.15 on caustic SCC.)

c) For localized caustic gouging to occur, a concentrating mechanism must exist to build up the caustic strength
or salt concentration.

Caustic can become concentrated by departure from nucleate boiling (DNB), evaporation, and deposition
of salts.

Higher temperatures help produce a concentrating mechanism, thereby increasing the corrosivity of the
solution while also generally increasing the corrosion rate.

d) Some contaminants, such as chlorides and hypochlorites, are known to increase the corrosivity of caustic
solutions.

e) Heat tracing may sometimes contribute to this problem.

3.14.4 Affected Units or Equipment

a) Localized caustic corrosion (caustic gouging) is most often associated with boilers and steam-generating
equipment including heat exchangers. This also applies to steam-generating equipment in H2 manufacturing
units and steam generators within other process units.

b) Similar concentrating effects of caustic can occur where caustic is added to crude unit feed.
70 API RECOMMENDED PRACTICE 571

Accelerated localized corrosion can occur in preheat exchangers, furnace tubes, and transfer lines, if the
caustic is not effectively mixed in the oil stream.

c) Units that use caustic for removing sulfur compounds from process streams can also be subject to caustic
corrosion.

d) Heat-traced tanks used for caustic storage and caustic feed equipment near the process injection location
can suffer caustic corrosion if temperatures get too high.

3.14.5 Appearance or Morphology of Damage

a) Caustic gouging is typically characterized by localized metal loss that may appear as grooves in a boiler tube
or locally thinned areas under insulating deposits. (Figure 3-14-1 and Figure 3-14-2)

b) Deposits may fill corroded depressions and mask damage below. Probing suspect areas with a sharp
instrument may be required.

c) Localized gouging may result along a waterline where corrosives concentrate. In vertical tubes, this may
appear as a circumferential groove.

d) In horizontal or sloped tubes, grooving may appear at the top of the tube or as longitudinal grooves on
opposite sides of the tube.

e) Corrosion of carbon steel in high-concentration caustic at elevated temperatures will be generalized but likely
confined to the location of the high temperature, e.g. next to heat tracing.

3.14.6 Prevention/Mitigation

a) In steam-generating equipment, caustic corrosion is best prevented through proper design. Damage can be
minimized by reducing the amount of free caustic, by ensuring adequate water flooding and water flow, by
ensuring proper burner management to minimize hot spots on heater tubes, and by minimizing the ingress
of alkaline producing salts into condensers.

b) In process equipment, caustic injection facilities should be designed to allow proper mixing and adequate
dilution of caustic in order to avoid the concentration of caustic on hot metal surfaces.

c) Carbon steel (and stainless steels) have serious corrosion problems in high-strength caustic solutions at
elevated temperatures. Alloy 400 and some other nickel-based alloys exhibit much lower corrosion rates.

3.14.7 Inspection and Monitoring

a) General Corrosion—UT using a straight beam or UT scanning or other similar techniques can measure
general loss.

b) Localized Corrosion—Manual UT, including UT scanning, or AUT can be used. Angle beam (SWUT or
PAUT) or TOFD may be necessary to determine the extent of localized corrosion. RT has also been used
within the limits of the technique.

c) Permanently mounted thickness monitoring sensors can be used.

d) Heat or steam tracing can cause localized corrosion at the point of contact due to locally high temperatures
or improper installation. This is an area to focus on for inspection.

e) Caustic injection sites should be examined and monitored as discussed in API 570 and API 574.

f) When internal access is not available (e.g. steam equipment, tubing, small-diameter equipment, or
equipment with ports), VT may be performed using a boroscope.
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 71

3.14.8 Related Mechanisms

Caustic SCC (3.15). Caustic gouging has also been referred to as ductile gouging.

Figure 3-14-1—ID deposits on carbon steel boiler tube with damage due to caustic corrosion.

Figure 3-14-2—Cross section of tube in Figure 3-14-1 showing

localized attack due to caustic corrosion.
72 API RECOMMENDED PRACTICE 571

Caustic SCC is a form of stress corrosion cracking characterized by that

3.15 Caustic Stress Corrosion Cracking _____________occur in piping and equipment exposed to caustic, primarily adjacent
to non‐PWHT’d welds.
3.15.1 Description of Damage Answer: surface‐initiated Cracks

Caustic SCC is characterized by surface-initiated cracks that occur in piping and equipment exposed to caustic
(alkaline hydroxide solutions) at elevated temperature, primarily adjacent to non-PWHT’d welds. It is a form of
ASCC. The temperature above which caustic SCC occurs depends on the concentration of the caustic solution.

3.15.2 Affected Materials

Carbon steel, low-alloy steels, and 300 series SS are susceptible. Duplex stainless steels are also susceptible
but have shown improved resistance compared to the 300 series SS. Nickel-based alloys are more resistant.

3.15.3 Critical Factors

a) Susceptibility to caustic SCC in caustic soda (NaOH) and caustic potash (KOH) solutions is a function of
caustic strength, metal temperature, and stress level.

b) Increasing caustic concentration and increasing temperature increase the likelihood and rate of cracking.
Conditions likely to result in cracking have been established through plant experience and are presented in
Figure 3-15-1.

c) Cracking can occur at low caustic levels if a concentrating mechanism is present. In such cases, caustic
concentrations of 50 ppm to 100 ppm are sufficient to cause cracking.

d) Residual stresses from welding (in non-stress-relieved welds) or from cold working (such as bending and
forming) will cause cracking, and these high residual stresses are what typically lead to caustic SCC. (Figure
3-15-2 to Figure 3-15-8) Applied stresses, e.g. from pressure or mechanical loading, can also cause caustic
SCC, but this is uncommon since applied stresses are normally low relative to the yield point and are lower
than residual stresses from welding or forming.

e) Thermal stress relief (PWHT) is effective in preventing caustic SCC. (Figure 3-15-1)

f) Crack propagation rates increase dramatically with temperature, and cracks can grow through wall in a matter
of hours during temperature excursions, especially in concentrated caustic or if conditions promote caustic
concentration. Concentration can occur as the result of alternating wet and dry conditions, localized hot spots,
or high-temperature steam out.

g) Special care must be taken with steam tracing or heat tracing design as well as steam out of non-PWHT’d
piping and equipment.

h) Contaminants in the caustic solution, especially sulfides, regardless of concentration, will increase the
likelihood of SCC in non-PWHT’d carbon steel, including in the lower temperature area (area “A”) in
Figure 3-15-1.

3.15.4 Affected Units or Equipment

a) Caustic SCC can occur in non-stress-relieved piping and equipment that handles caustic, including H2S and
mercaptan removal units, as well as equipment that uses caustic for neutralization in sulfuric acid alkylation
units and HF alkylation units. Caustic is sometimes injected into the feed to the crude tower for chloride
control.

b) Failures have occurred in improperly heat-traced piping or equipment as well as heating coils and other heat
transfer equipment.

c) Caustic SCC can occur in equipment as the result of steam cleaning after being in caustic service.

Caustic stress corrosion cracking Failures have occurred in improperly heat‐traced piping or equipment as well as_________.} /{Caustic stress corrosion cracking occurs
in equipment as well as___________.}
Answer: heating coils and other heat transfer equipment
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 73

d) Traces of caustic can become concentrated in BFW and can result in caustic SCC of boiler tubes that
alternate between wet and dry conditions due to overfiring. It can also occur in superheaters due to steam
drum carryover.

e) Cracking can occur in boilers at rolled tube joints due to caustic concentrating between the tube and
tubesheet. (Figure 3-15-4)

f) Caustic SCC can also occur as the result of unintended carryover of caustic into equipment not designed to
handle hot caustic (e.g. not stress relieved), such as steam condensate piping or process equipment
downstream of a caustic treating section of a process unit.

3.15.5 Appearance or Morphology of Damage

a) Caustic SCC typically propagates parallel to the weld in adjacent base metal, i.e. in the zone of highest
welding residual stress, but can also occur in the weld deposit or HAZ and can be transverse to the weld.

b) The pattern of cracking observed on the steel surface is sometimes described as a spider web of small cracks
that often initiate at or interconnect with weld-related flaws that serve as local stress risers.

c) Cracks can be confirmed through metallographic examination. Cracks are typically branched and
predominantly intergranular. Cracking that occurs in as-welded carbon steel typically appears as a network
of very fine, oxide-filled cracks.

d) Cracking in 300 series SS is most often transgranular but can be intergranular even in non-sensitized
material. When transgranular, it can be difficult to distinguish from Cl− SCC. Caustic SCC should exhibit a
black magnetite layer on the crack surface, whereas Cl− SCC should not produce that type of oxide scale.

e) Similarly, caustic SCC of nickel-based alloys has been observed as either intergranular (Figure 3-15-9) or
transgranular (Figure 3-15-10).

3.15.6 Prevention/Mitigation

a) Cracking can be effectively prevented by means of a stress-relieving heat treatment (e.g. PWHT). A heat
treatment at 1150 °F (620 °C) minimum with a minimum holding time of 1 hr is considered an effective stress
relieving heat treatment for carbon steel. The same requirement applies to repair welds and to internal and
external attachment welds.

In contaminated caustic solutions, stress relief may be needed to prevent cracking of carbon steel even
at low, otherwise “safe” temperatures (area “A” in Figure 3-15-1).

b) 300 series SS offer little advantage in resistance to cracking over carbon steel.

c) Nickel-based alloys are more resistant to cracking and may be required at higher temperatures and/or caustic
concentrations. However, caustic SCC of these alloys has been observed at high temperatures that promote
the formation of molten caustic in the absence of free water [604 °F (318 °C), at atmospheric pressure]. This
damage has sometimes been referred to as molten caustic cracking.

d) Steam out of non-PWHT’d carbon steel piping and equipment should be avoided. Where necessary,
equipment should be water washed before steaming out, and only low-pressure steam should be used for
short periods of time to minimize exposure.

e) Proper design and operation of the injection system is required to ensure that caustic is properly dispersed
before entering the high-temperature crude preheat system.

f) Ensure all soda ash (sodium carbonate) solution that may have been used as a protective measure against
polythionic acid stress corrosion cracking (PTA SCC) in 300 series SS equipment is drained prior to heating
up as this soda ash can result in caustic SCC of 300 series SS as well as Alloy 800 and Alloy 825 as the
water is boiled away.
74 API RECOMMENDED PRACTICE 571

3.15.7 Inspection and Monitoring

a) WFMT, ACFM, and ECT can be effective techniques to detect these surface-breaking cracks. Proper surface
preparation is necessary to ensure cracking is not masked by blending or smearing metal into the cracks.
The method of surface preparation is dependent upon the specific technique.

b) Angle beam ultrasonic techniques (SWUT and PAUT) can be effective to detect and size cracks. These
ultrasonic techniques can be used to periodically monitor crack growth.

c) PT or MT can be effective. PT may not be effective for finding tight cracks, because the cracks are oxide
filled.

d) RT may not be effective in detecting fine, tight cracks.

e) AET can be used for locating cracks and monitoring crack growth.

f) Severe cracking can at times be identified visually.

3.15.8 Related Mechanisms

Amine SCC (3.3) and carbonate SCC (3.12) are two other similar forms of ASCC. Caustic SCC has also been
called caustic embrittlement, but this is a misnomer and an obsolete term. Caustic SCC is a SCC mechanism,
not an embrittlement mechanism.
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 75

Source: NACE SP0403-2015 (formerly RP0403), Avoiding Caustic Stress Corrosion Cracking of Refinery Equipment
and Piping, from NACE International. For more information, see https://www.nace.org/home.

Figure 3-15-1—Recommended operating limits for carbon steel in caustic service. (Reference 4)
76 API RECOMMENDED PRACTICE 571

Figure 3-15-2—Cracking initiating on the inside surface of a non-stress-relieved carbon steel heat
exchanger bend after 8 years in 15 % to 20 % caustic service at 140 °F to 240 °F (60 °C to 115 °C).

Figure 3-15-3—Photomicrograph of a crack in the tube shown in Figure 3-15-2.

 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 77

Figure 3-15-4—Cracking in a boiler tubesheet due to caustic

concentrating between the tube and the tubesheet.

Figure 3-15-5—Photomicrograph of a crack in the tubesheet shown in Figure 3-15-4.

78 API RECOMMENDED PRACTICE 571

Figure 3-15-6—Photomicrograph of caustic cracking initiating on the ID of a carbon steel socket weld
in non-PWHT’d piping in a suction drum downstream of a caustic scrubber. Unetched.

Figure 3-15-7—Figure 3-15-6 in the etched condition.

 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 79

Figure 3-15-8—Stainless steel expansion bellows from a steam-driven

turbine previously subjected to a caustic carryover upset condition.

Figure 3-15-9—Micrograph showing intergranular caustic SCC in an expansion joint

bellows constructed of Alloy 625 in a 400 psig steam superheater. (Reference 4)
80 API RECOMMENDED PRACTICE 571

Figure 3-15-10—Micrograph showing transgranular caustic

SCC in Alloy 825. Magnification 200X. (Reference 5)
86 API RECOMMENDED PRACTICE 571

3.17 Chloride Stress Corrosion Cracking

3.17.1 Description of Damage

Surface initiated cracking of 300 series SS and some nickel-based alloys under the combined action of tensile
stress, temperature, and an aqueous chloride environment. It is also referred to as chloride cracking.

3.17.2 Affected Materials

a) All 300 series SS are highly susceptible. Welds in 300 series SS normally contain some ferrite, producing a
duplex structure that is usually more resistant to chloride stress corrosion cracking (Cl– SCC) than the base
metal.

b) Duplex stainless steels are more resistant but still susceptible.

c) Nickel-based alloys are highly resistant but not immune.

3.17.3 Critical Factors

a) Chloride content, temperature, pH, tensile stress, presence of oxygen, and alloy composition are critical
factors.

b) Cl− SCC is caused by the inorganic chloride ion (Cl−) (or other inorganic halide ions such as bromide, in which
case it might be named differently). Organic chlorides will not directly cause Cl− SCC, but they can, and
typically do, produce ionic, inorganic chlorides by the processes of hydrolysis or thermal decomposition
(pyrolysis). Therefore, organic chlorides can lead to Cl− SCC.

c) Increasing levels of chloride increase the likelihood of cracking.

No practical lower limit for chlorides exists because of the potential for chlorides to concentrate. For
example, heat transfer conditions, as on the surface of exchanger tubes, significantly increase cracking
potential. Repetitive wetting and drying situations, including alternating steam and water, can also lead
to cracking.

Non-condensing systems will be a particular concern, because the chlorides cannot be removed with the
water phase.

d) Increasing temperatures increase the potential for cracking, as long as the other required elements (stress
and aqueous chloride solution) are present concurrently.

Although there are exceptions at lower temperatures and even ambient temperature, particularly with
highly cold worked or sensitized materials, cracking usually occurs at metal temperatures above about
140 °F (60 °C), and experience has shown this to be a useful temperature limit guideline for fixed
equipment in the refining industry.

e) The potential for cracking increases at lower pH; however, SCC usually does not occur at pH values below
2. At these lower pH values, uniform corrosion generally predominates. Cl− SCC tendency decreases toward
the alkaline pH region; however, stainless steels and some nickel-based alloys (e.g. Alloy 800 and Alloy 825)
can suffer caustic SCC in alkaline environments. (See 3.15.)

f) The tensile stress may be applied or residual. The most common area of concern is non-stress-relieved
welds. However, highly stressed or cold worked components, such as expansion bellows, are also highly
susceptible to cracking.

g) Oxygen dissolved in the water normally accelerates SCC, but it is not clear whether there is an oxygen
concentration threshold below which Cl− SCC does not occur. Other oxidizers in addition to oxygen (e.g. CO
and CO2) can also enhance Cl− SCC.
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 87

h) Nickel content of the alloy has a major effect on resistance. The greatest susceptibility occurs in stainless
steels with a nickel content of 8 % to 12 %.

Alloys with nickel contents above 35 % are highly resistant, and alloys above 45 % are nearly immune
in refining applications, but cracking can still occur in severe conditions.

Low-nickel stainless steels, such as the duplex (ferrite-austenite) stainless steels, have improved
resistance over the 300 series SS but are not immune.

3.17.4 Affected Units or Equipment

a) Most non-stress-relieved 300 series SS piping and equipment in any process unit are susceptible to Cl− SCC.
Even if the process side will not cause SCC, if the piping or equipment operates above 140 °F (60 °C), it is
likely exposed to alternating wet and dry conditions on the outside.

b) Chloride cracking has occurred in water-cooled condensers and on the process side of crude tower overhead
condensers.

c) Stainless steel drains in hydroprocessing units are susceptible to cracking, particularly during start-up, if not
properly purged.

d) Bellows and instrument tubing, particularly those associated with hydrogen recycle streams contaminated
with chlorides, can be affected.

e) External Cl− SCC can occur on insulated 300 series SS surfaces when insulation gets wet.

The operating temperature range of most concern for external Cl− SCC is 140 °F (60 °C) to 400 °F
(205 °C).

f) Chloride cracking has occurred in boiler drain lines.

g) Highly localized Cl− SCC has occurred in exchanger tube bundles where the bulk fluid temperature inside
the tubes was above the water dew point. Cold fluid entering the shell side caused shock condensation within
the tubes and resultant chloride cracking on the tube side.

h) Units processing or co-processing bio-based or renewable feedstocks (biomass, natural fats and oils, etc.)
are particularly susceptible to Cl− SCC due to high levels of organic chlorides converting to inorganic chlorides
in the reactor effluent.

3.17.5 Appearance or Morphology of Damage

a) Surface-breaking cracks can occur from the process side or externally under insulation. (Figure 3-17-1 and
Figure 3-17-2)

b) The component usually shows no visible signs of corrosion.

c) Characteristic stress corrosion cracks have many branches and may be visually detectable as spider web or
craze cracking on the surface. (Figure 3-17-3)

d) Metallography of cracked samples typically shows branched, transgranular cracks. (Figure 3-17-4 to Figure
3-17-6)

e) Cracking of sensitized 300 series SS may be intergranular.

f) Cl− SCC in nickel-based alloys, which can occur under severe conditions, appears similar to Cl− SCC in
stainless steel. (Figure 3-17-7)

g) Fracture surfaces typically have a brittle appearance.

88 API RECOMMENDED PRACTICE 571

3.17.6 Prevention/Mitigation

a) Materials of construction resistant to Cl− SCC should be used. Carbon steels, low-alloy steels, and 400 series
SS are not susceptible to Cl− SCC.

b) When hydrotesting, low-chloride-content water should be used, followed quickly by thorough dryout.

c) A suitable coating should be applied to stainless steel piping and equipment prior to insulating.

Shrink-wrapped PVC labels, coatings, or label adhesives with high levels of chlorides or other halogen
ions should be avoided.

d) Avoid designs that create stagnant regions where chlorides can deposit or concentrate.

e) Although not a standard or common refining industry practice, a suitable high-temperature stress relief of 300
series SS after fabrication will reduce residual stresses. However, consideration should be given to the
possible effects of sensitization that may occur, increasing susceptibility to PTA SCC (3.52), possible
distortion problems, and the potential for stress relaxation cracking (SRC) (3.54).

f) Avoid exchanger designs with 300 series SS steel tubes and a high delta T between the shell and tube side
where localized condensation can occur on or in the tubes.

g) Avoid contact with high-chloride water run-off that can occur with the use of salts for snow and ice melting.

3.17.7 Inspection and Monitoring

Cracking may be either process side or external (usually under insulation that has become wet or where
external water can collect), and it should be understood on which side the damage is occurring in order to
properly develop an inspection plan. Cl− SCC may be detected using the following methods.

a) VT can be used to find advanced stages of cracking.

b) PT can be used for Cl− SCC. However, extremely fine cracks may be difficult to detect with PT. Special
surface preparation methods, including polishing or high-pressure water blast, may be required in some
cases, especially in high-pressure services.

c) ECT inspection methods can be used on condenser tubes as well as piping and pressure vessels.

d) Angle beam UT (SWUT and PAUT) from the opposite wall can be used for crack detection; however,
detection and characterization of the cracking will be difficult due to the craze-cracked, multi-branched
appearance of Cl− SCC.

e) RT is often not sensitive enough to detect cracks except in advanced stages where a sufficient network of
cracks has developed.

3.17.8 Related Mechanisms

Caustic SCC (3.15), PTA SCC (3.52), and brine corrosion (3.10).
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 89

Figure 3-17-1—External cracking of Type 304 SS instrument tubing under insulation.

Figure 3-17-2—External cracking of Type 304 SS instrument tubing under insulation.

90 API RECOMMENDED PRACTICE 571

Figure 3-17-3—Cracking on the shell side of a Type 316L SS tube in steam service at 450 °F (230 °C)
showing tight cracks with a crazed or spider web appearance.

Figure 3-17-4—Photomicrograph of a cross section of the tube in Figure 3-17-3

showing fine branching cracks. (Magnification 50X, unetched.)
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 91

Figure 3-17-5—Another photomicrograph of a cracked tube illustrating the

transgranular mode of cracking initiating at the surface. (Etched.)

Figure 3-17-6—Cl− SCC on the thread surface of a failed 303 SS bolt.

92 API RECOMMENDED PRACTICE 571

(a)

(b)

(c)

Figure 3-17-7—Severe cracking of a finned Alloy C-276 tube in a deethanizer reboiler after 8 years
of service due to ammonium chloride carryover. (a) Hundreds of cracks initiated on the OD
(process side) of the tube. (b) The cracks were associated with the cold-worked portion of
the tubes at the fins. (c) The cracks were branching and transgranular, typical of Cl− SCC.
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 111

3.22 Corrosion Under Insulation

3.22.1 Description of Damage

Corrosion of piping, pressure vessels, and structural components resulting from water trapped under insulation
or fireproofing.

3.22.2 Affected Materials

Carbon steel, low-alloy steels, 300 series SS, 400 series SS, and duplex stainless steels.

3.22.3 Critical Factors

a) Temperature, duration of wetting, design of the insulation system, insulation type, and environment are critical
factors.

Corrosion rates increase with increasing metal temperature up to the point where the water evaporates
quickly. While water boils or steams off above the boiling temperature, 212 °F (100 °C), it does not do so
instantaneously. It takes some amount of time for water to boil off and wet insulation to dry out. During this
time, the metal is corroding. The higher the temperature above the boiling point, the faster the water will
evaporate and the insulation will dry out. However, with a high enough rate of wetting and replenishment
of the water in the wet insulation, CUI can occur on equipment operating at virtually any temperature of
practical concern in refining.

In most situations, and as a practical matter, refiners generally focus their CUI management efforts on
insulated carbon steel, low-alloy steel, and 400 series SS equipment operating between 10 °F (−12 °C)
and 350 °F (175 °C).

For 300 series SS, where Cl− SCC is the concern, refiners generally focus on the temperature range of
140 °F (60 °C) to 350 °F (175 °C).

For duplex stainless steel, where Cl− SCC is the concern, refiners generally focus on the temperature
range of 280 °F (140 °C) to 350 °F (175 °C).

b) The extent of CUI attack depends on the total amount of time the equipment remains wet from exposure to
wet insulation. Therefore, while a higher operating temperature will result in a higher corrosion rate, the total
amount of attack over a long period of time may occur at a lower temperature if the metal remains wet for
significantly longer periods of time at the lower temperature. This is one of the reasons why CUI corrosion
rates are difficult to predict.

c) Poor design or installation of insulation systems that allow water to become trapped will increase CUI.

d) Insulating materials that wick moisture can hold water and be more prone to causing extensive CUI.

e) Insulating materials that dry out slowly can be more prone to causing extensive CUI.

f) Cyclic thermal operation or intermittent service can increase corrosion.

g) Equipment that operates below the water dew point tends to condense water on the metal surface, thus
providing a wet environment and increasing the risk of corrosion.

h) Damage is aggravated by contaminants that may be leached out of the insulation, such as chlorides.

i) Plants located in areas with high annual rainfall or warmer marine locations are more prone to CUI than
plants located in cool and dry or warm and dry locations.

j) Environments that provide airborne contaminants such as chlorides (e.g. from marine environments or
cooling tower drift) or SO2 (e.g. from stack emissions) can accelerate corrosion.
112 API RECOMMENDED PRACTICE 571

3.22.4 Affected Units or Equipment

a) All insulated piping and equipment are susceptible to CUI under the conditions noted above, even piping and
equipment where the insulation system appears to be in good condition and no visual signs of corrosion are
present.

b) Examples of locations where CUI can occur are listed below.

CUI can be found on equipment with damaged insulation, insulation jacketing, vapor barriers,
weatherproofing or mastic, or where caulking has hardened, separated, or is missing.

CUI can occur where water gains access at protrusions through the insulation or at insulation termination
points such as flanges.

Piping components and locations that are particularly susceptible include dead-legs (vents, drains, and
other similar items), pipe hangers and other supports, valves and fittings with irregular insulation
surfaces, bolted-on pipe shoes, steam tracing tube or heat tracing wire penetrations, at the terminations
of insulation at flanges or other piping components, at the termination of insulation in vertical pipe, and
the first few feet of a horizontal pipe run adjacent to the bottom of a vertical run.

Piping or equipment with damaged and leaking steam tracing is susceptible.

Vibrating piping systems have a tendency to inflict damage to insulation jacketing providing a path for
water ingress.

Insulation jacketing seams located on the top of horizontal piping or improperly lapped or sealed
insulation jacketing can lead to CUI.

Locations where moisture or trapped water will naturally collect due to gravity drainage before
evaporating such as low points in piping runs and insulation support rings on vertical columns, as well
as improperly terminated fireproofing.

Equipment designed with insulation support rings welded directly to the vessel wall (i.e. with no standoff)
can be susceptible, particularly around ladder and platform clips, lifting lugs, nozzles, and stiffener rings.

CUI can occur in carbon or low-alloy steel flanges, bolting, and other components under insulation in
high-alloy piping systems.

Locations where insulation plugs have been removed to permit piping thickness measurements on
insulated piping and equipment are a potential source of water ingress.

Where piping and equipment have been coated beneath the insulation, localized CUI can still occur
where the coating has deteriorated or been damaged.

Equipment subjected to long-term or frequent water spray, e.g. from firefighting, fire equipment testing,
or supplemental externally applied cooling, is highly susceptible to CUI.

300 series SS equipment insulated with older calcium silicate insulation, which is known to contain high
levels of chlorides, can suffer pitting, crevice corrosion, and Cl− SCC.

3.22.5 Appearance or Morphology of Damage

a) Carbon steel and low-alloy steels are subject to corrosion having a rough, uneven, somewhat pitted
appearance, usually covered with a loose, flaky, non-protective scale attached. The corrosion will be localized
to wherever the metal has been kept wet by wet insulation. (Figure 3-22-1 to Figure 3-22-8)

b) In some cases, the corrosion can appear to be carbuncle-type pitting (usually found under failed coating).

c) 300 series SS are subject to SCC if chlorides are present. While the duplex stainless steels are less
susceptible, SCC failures have occurred in duplex stainless steel due to CUI.
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 113

d) 300 series SS and duplex stainless steel are subject to pitting and crevice corrosion.

e) Telltale signs of CUI include insulation jacketing damage, bulges or staining of the insulation or jacketing,
missing bands, coating damage, or vegetation growing out of the insulation. Bulges may indicate corrosion
product buildup.

3.22.6 Prevention/Mitigation

a) Since most construction materials used in refining are susceptible to CUI damage, mitigation is best achieved
by applying an appropriate coating to the equipment prior to insulating.

High-quality, immersion-resistant nonmetallic coatings, properly applied to the surfaces to be insulated,

can provide long-term protection.

Flame-sprayed aluminum coatings have been used on carbon steels. The coating corrodes preferentially
by galvanic action, thereby protecting the base metal.

b) Insulation, insulation jacketing, sealants, and vapor barriers should be properly maintained to prevent
moisture ingress.

c) Thin aluminum foil wrapped on stainless steel piping and equipment beneath the insulation can provide an
effective barrier, partly due to the galvanic effect of the aluminum in preventing Cl− SCC in stainless steel.

d) Careful selection of insulating materials is important. Both water absorption properties and water retention
characteristics are important and should be considered. Some insulating materials absorb little water but still
trap water against the pipe or equipment for an extended time because water removal is slow. While closed-
cell foam glass materials will hold less water and, therefore, might be less prone to causing CUI, studies
show that an open cell structure provides a path for water vapor to escape faster, allowing the insulation to
dry quicker. Faster drying time, corresponding to less metal wetting time, should help mitigate CUI.

Types of open cell insulation that limit and delay water ingress have been developed.

Water absorption and retention properties of insulation materials can be tested per EN 13472 or ASTM
C1134.

e) Insulation with added corrosion inhibitor is available.

f) Low-chloride insulation should be used on 300 series SS to minimize the potential for pitting and Cl− SCC.

Some manufacturers supply insulation certified to be low chloride. Thermal insulation materials can be
tested per ASTM C871 to evaluate chloride content and/or ensure it satisfies a specified limit.

g) Insulation plugs removed for UT thickness measurements should be promptly replaced and sealed. Several
types of removable plugs that permit inspection and identification of inspection points are commercially
available.

h) Consider available alternatives in order to avoid the use of insulation where practical.

Personnel protection from hot piping can be provided using metal-cage-type standoffs rather than
insulation.

It is not usually possible to modify operating conditions; however, consideration should be given to
removing the insulation on equipment where heat conservation is not as important.

3.22.7 Inspection and Monitoring

a) An inspection plan for CUI should be a structured, systematic approach starting with prediction and analysis
per the CUI planning information contained in API 510, API 570, and API 583. [API 583 was created
specifically for CUI/CUF (corrosion under fireproofing) and should be referenced for a deeper understanding
of inspection for these damage mechanisms.] The inspection plan should consider:
114 API RECOMMENDED PRACTICE 571

history of CUI leaks,

operating temperatures that may give rise to CUI,

type and age/condition of coating, and

type, age, and condition of the insulation material.

b) Additionally, an external VT of the equipment, looking for evidence of insulation system damage, mastic
and/or sealant damage, signs of water penetration, rust in gravity drain areas on equipment and piping, and
signs of process fluid leaks, will help prioritize the effort.

c) Although external insulation may appear to be in good condition, CUI damage may still be occurring in
isolated areas not thought to be susceptible. The owner/user generally determines the extent of CUI
inspection, including the extent of insulation removal for inspection, based on inspection and CUI history and
other factors as described above.

An effective way to find all CUI damage is complete removal of insulation and inspection for damage
using VT, UT, and/or a pit gage, as applicable, for determining remaining thickness, or PT to examine
for external Cl− SCC of austenitic stainless steels.

Inspection by RT (density and/or profile) or UT thickness inspection (e.g. using high-resolution pigging)
can also provide a high level of CUI detection confidence, depending on the extent of inspection, i.e. the
percent of potentially affected piping inspected.

In some instances, insulation “windowing” can be used to remove insulation in selected areas thought to
be more susceptible to CUI damage than others and inspecting for damage using VT, UT, and/or a pit
gage, as applicable, for determining remaining thickness, or PT to examine for external Cl− SCC of
austenitic stainless steels. However, this may be less effective than complete insulation removal.

d) Non-invasive, commercially available methods can be used to identify either wet insulation or CUI damage
under the insulation without removing the insulation; however, these methods should not be expected to find
100 % of the damage. Each of these methods is discussed in API 583, including advantages and
disadvantages of each. Most are screening techniques that may help identify where there is a higher
probability of CUI damage and where insulation stripping may be needed to further assess and quantify the
damage. These methods include, but may not be limited to:

GWT;

RT (including profile, density, flash, radiometric profiling, real-time, computed, and digital);

PEC;

neutron backscatter (for identifying wet insulation); and

infrared thermography imaging (for identifying wet insulation).

e) Common areas of higher CUI concern in process units are high-moisture areas such as those down-wind
from cooling towers (the drift zone), near steam vents, under deluge systems, exposed to acid vapors, or
near supplemental cooling with water spray.

3.22.8 Related Mechanisms

Atmospheric corrosion (3.8), oxidation (3.48), oxygenated water corrosion (3.49), concentration cell corrosion
(3.19), and Cl− SCC (3.17).
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 115

Figure 3-22-1—Piping tee in a 1000 psig ethylene line before insulation removal.
116 API RECOMMENDED PRACTICE 571

Figure 3-22-2—Close-up of the tee in Figure 3-21-1 after insulation removal.

Figure 3-22-3—CUI of a 30-in. carbon steel butadiene line showing highly localized corrosion that
could only be found by stripping the entire line. Note the 0.25-in. (6.5-mm) diameter hole at arrow.
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 117

Figure 3-22-4—CUI of a nozzle on the bottom head of a pressure vessel.

Figure 3-22-5—CUI of a nozzle on the top head of a pressure vessel.

118 API RECOMMENDED PRACTICE 571

Figure 3-22-6—CUI of a vessel wall. Note the leak at the arrow.

Figure 3-22-7—CUI at attachment supports and on the vessel head.

DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 119

Figure 3-22-8—CUI of a carbon steel level bridle.

 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 225

3.43 Mechanical Fatigue (Including Vibration-induced Fatigue)

3.43.1 Description of Damage

a) Fatigue cracking is a mechanical form of degradation that occurs when a component is exposed to cyclical
stresses for an extended period, e.g. from dynamic loading due to vibration, water hammer, or unstable fluid
flow, often resulting in sudden, unexpected thru-wall cracking.

b) These stresses can arise from either mechanical loading or thermal cycling and are typically well below the
yield strength of the material. This section focuses on mechanical loading, while the effects of thermal cycling
are covered in 3.64 on thermal fatigue.

3.43.2 Affected Materials

All engineering alloys are subject to fatigue cracking although the stress levels and number of cycles necessary
to cause failure can vary by material.

3.43.3 Critical Factors

a) Geometry, stress level, number of cycles, and material properties (strength, hardness, microstructure) are
predominant factors in determining the fatigue resistance of a component. The amplitude and frequency of
vibrations (related to stress level and number of cycles) in vibrating equipment such as piping are also critical
factors. There is a high likelihood of cracking when the input vibrational load is synchronous or nearly
synchronizes with the natural or harmonic frequency of the component.

b) Design Factors—Fatigue cracks usually initiate on the surface at notches or stress risers under cyclic loading.
For this reason, design of a component is the most important factor in determining a component’s resistance
to fatigue cracking. Common surface features that can lead to the initiation of fatigue cracks, because they
act as stress concentrations, include:

key holes on drive shafts of rotating equipment,

mechanical notches (sharp corners or groves),

weld joint flaws and/or mismatches,

tool markings,

grinding marks,

lips on drilled holes,

thread root notches, and

corrosion.

In vibrating or shaking equipment, especially piping, a lack of or improperly placed support or stiffening can
lead to cracks initiating at the types of stress risers or notches listed above. The normal toe or edge of a
properly made, Code-acceptable weld can provide the stress concentration to initiate a fatigue crack in badly
vibrating or shaking equipment. Often the cracks will form at the location(s) where the vibrating or shaking
equipment is fixed and prevented from moving with the adjacent component. This situation most often needs
to be addressed by reducing the amount of vibration or shaking.

c) Metallurgical issues and microstructure.

Some materials such as titanium, carbon steel, and low-alloy steel have an “endurance limit.” In such
cases, the number of cycles to fatigue fracture increases with decreasing stress amplitude until a stress
226 API RECOMMENDED PRACTICE 571

amplitude endurance limit is reached below which fatigue cracking will not occur, regardless of the
number of cycles.

For alloys with endurance limits, there is a correlation between ultimate tensile strength (UTS) and the
minimum stress amplitude necessary to initiate fatigue cracking, i.e. the endurance limit. The ratio of
endurance limit to UTS is typically between 0.4 and 0.5.

300 series SS, 400 series SS, aluminum, and most other non-ferrous alloys have a fatigue characteristic
that does not exhibit an endurance limit. This means that fatigue fracture can be achieved under cyclic
loading eventually, given enough cycles, regardless of stress amplitude. Maximum cyclic stress
amplitude for design is selected by determining the cyclic stress necessary to cause fracture in the
number of cycles the component needs to withstand in its lifetime. This is typically 106 to 107 cycles.

The endurance limit described in Item 1 above primarily applies to smooth bars and similar configurations
as might be found in a pump shaft. For welded components, such as piping or other situations where
inherent discontinuities, flaws, or other high stress concentrations exist, the crack initiation portion of
fatigue life is essentially eliminated, leaving only the crack growth portion. This situation effectively
eliminates the existence of the endurance limit. Thus, the concept of the endurance limit generally cannot
be taken advantage of with vibrating or shaking equipment.

Inclusions found in metal can have an accelerating effect on fatigue cracking. This is of importance when
dealing with older, “dirty” steels or weldments, as these often have inclusions and discontinuities that can
degrade fatigue resistance.

Heat treatment can have an effect on fatigue resistance of a metal. In general, finer-grained
microstructures tend to perform better than coarse grained. Heat treatments such as quenching and
tempering can improve fatigue resistance of carbon and low-alloy steels.

3.43.4 Affected Units or Equipment

a) Socket welds and small-bore piping (e.g. bypass lines, minimum flow loops) associated with or near pumps,
compressors, or other rotating or reciprocating equipment that are not properly gusseted and supported.

b) Small branch connections with unsupported valves or controllers that may see vibration from adjacent
equipment and/or wind. For small components, resonance can also produce a cyclic load and should be
taken into consideration during design and reviewed for potential problems after installation.

c) Safety-relief valves that are subject to chatter, premature pop-off, fretting, and failure to operate properly.

d) High-pressure-drop control valves or steam-reducing stations that can cause serious vibration problems in
connected piping.

e) Rotating shafts on centrifugal pumps and compressors that have stress concentrations due to changes in
radii and keyways.

f) Heat exchanger tubes that may be susceptible to vortex shedding.

g) Pressure swing absorber vessels in hydrogen purification units.

h) Transient conditions (such as start-ups, shutdowns, upsets, etc.) can create intermittent, but severe, vibrating
conditions.

3.43.5 Appearance or Morphology of Damage

a) Damage is usually in the form of a crack emanating from a point of high stress concentration or discontinuity
such as thread, a weld (Figure 3-43-1 to Figure 3-43-4), or the corner of a keyway in a shaft.
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 227

b) The signature mark of a fatigue failure is a “clam-shell”-type fingerprint that has concentric rings called “beach
marks” emanating from the crack initiation site (Figure 3-43-5 to Figure 3-43-8). This signature pattern results
from the “waves” of crack propagation that occur during cycles above the threshold loading. These concentric
cracks continue to propagate until the cross-sectional area is reduced to the point where failure due to tensile
overload occurs.

c) Cracks nucleating from a surface stress concentration or defect will typically result in a single “clam shell”
fingerprint. (Figure 3-43-8)

d) Cracks resulting from cyclical overstress of a component without one significant, isolated stress concentration
point will typically result in a fatigue failure with multiple points of nucleation and hence multiple “clam shell”
fingerprints. These multiple nucleation sites, often called “ratchet markings,” are the result of microscopic
yielding that occurs when the component is momentarily cycled above its yield strength. (Figure 3-43-9)

3.43.6 Prevention/Mitigation

a) Piping and other fixed equipment.

The best defense against fatigue cracking is good design that helps minimize stress concentration of
components that are in cyclic service.

Fatigue cracking in piping can usually be eliminated or reduced through proper design and the use of
properly placed support and vibration dampening equipment. Material upgrades are not usually a
solution.

Install gussets or stiffeners on small-bore connections so that they cannot move independently of the
larger pipe or other component to which they are connected. Eliminate unnecessary connections.

Vortex shedding can be minimized at the outlet of control valves and safety valves through proper side
branch sizing and flow stabilization techniques.

Vibration effects may be shifted when a vibrating section is anchored. Special studies may be necessary
before anchors or dampeners are provided, unless the vibration is eliminated by removing the source.

Assure good fit-up and smooth transitions for welds. Employ a gradual bore taper on the thicker
component when transitioning between different pipe schedules.

Minimize weld defects as these can accelerate fatigue cracking.

Minimize grinding marks, nicks, and gouges on the surface of components subject to cyclic loading.

Use low-stress stamps and marking tools.

b) Rotating equipment.

Allow for a generous radius along edges and corners, particularly in shaft keyways.

Remove any burrs or lips caused by machining.

Although fatigue cracking problems are generally addressed by design and fabrication improvements,
ensure that the metal selected has fatigue life sufficient for its intended cyclic service.

c) API 579-1/ASME FFS-1 contains useful information related to determining critical fatigue crack sizes and
assessing crack growth rates.

3.43.7 Inspection and Monitoring

In high cycle fatigue, the time required for a crack to initiate or grow sufficiently to be identifiable by NDE
228 API RECOMMENDED PRACTICE 571

methods can be a majority of the fatigue life, making detection before cracking and failure difficult. For this
reason, it is normally impractical to rely on NDE methods for routine, global inspection of fixed equipment to
avoid fatigue cracking failures. Frequent NDE in a focused program aimed at a specific, known problem area
can be used for finding cracks before failure, but this is not normally considered an effective, long-term
approach to managing the problem.

a) PT can be used to detect cracks open to the surface.

b) MT (including WFMT) can be used to detect cracks open to the surface or near the surface.

c) Angle beam (SWUT and PAUT) can be used to detect fatigue cracks at known or suspected areas of
concern, e.g. at stress concentrations and welded connections, and where cracking is internal, i.e. initiating
on the ID surface and not visible from the outside. In some situations, e.g. with very thick components,
compression wave UT may be needed.

d) Compression wave UT can detect cracking in bolts.

e) Vibration monitoring of rotating equipment may provide online detection of conditions that can result in shaft
failures due to out of balance conditions.

f) Piping oscillation, vibration, or water hammer, especially involving small-bore components that are not
adequately supported, is often visually apparent. Focus on weld joints and locations where the pipe is fixed
and prevented from moving. Pipe vibrations can be measured using special monitoring equipment.

g) Pipe supports and spring hangers should be checked on a regular schedule.

h) Audible sounds of vibration emanating from components such as control valves can be an indication of
conditions capable of causing fatigue cracks.

i) Damaged insulation jacketing may indicate excessive vibration.

3.43.8 Related Mechanisms

Thermal fatigue (3.64) and corrosion fatigue (3.21).

 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 229

Figure 3-43-1—Vibration induced fatigue of a 1-in. socket weld flange

in a thermal relief system shortly after start-up.

Figure 3-43-2—Cross-sectional view of the crack in the socket weld in Figure 3-41-1.
230 API RECOMMENDED PRACTICE 571

Figure 3-43-3—Fatigue crack in a 16-in. pipe-to-elbow weld in the fill line

of crude oil storage tank after 50 years in service.

Figure 3-43-4—A cross section through the weld showing the crack location.
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 231

Figure 3-43-5—Schematic of a fatigue fracture surface showing “beach marks.”

Figure 3-43-6—Compressor rod fracture surface showing “beach marks.”

232 API RECOMMENDED PRACTICE 571

Figure 3-43-7—Higher-magnification view of Figure 3-41-6 above showing “beach marks.”

Figure 3-43-8—Fatigue fracture surface of a carbon steel pipe.

 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 233

Figure 3-43-9—The surface of the fracture face of the crack shown in Figure 3-41-3 and Figure 3-41-4.
238 API RECOMMENDED PRACTICE 571

3.45 Microbiologically Influenced Corrosion

3.45.1 Description of Damage

Corrosion caused by living organisms such as bacteria, algae, or fungi. It is often associated with the presence
of tubercles or slimy organic substances. Often, the bacteria produce localized corrosion in the form of pitting or
crevice corrosion.

3.45.2 Affected Materials

Most common materials of construction including carbon and alloy steels, 300 series SS and 400 series SS,
aluminum alloys, copper alloys, and some nickel alloys. Titanium appears to be highly resistant.

3.45.3 Critical Factors

a) Microbiologically influenced corrosion (MIC) is found in aqueous environments. Occasionally it is found in

services where water is intermittently present. Stagnant or low-flow conditions allow and/or promote the
growth of microorganisms.

b) Because there are many types, organisms can survive and grow under a wide range of conditions including
lack of oxygen, light or dark, high salinity, pH range of 0 to 12, and temperatures from 0 °F to 235 °F (–15 °C
to 115 °C).

c) Systems may become “inoculated” by the introduction of organisms that multiply and spread unless
controlled.

d) Different organisms thrive on different nutrients including inorganic substances (e.g. sulfur, ammonia, iron,
sulfate compounds, and H2S) and organic substances (e.g. hydrocarbons and organic acids). In addition, all
organisms require a source of carbon, nitrogen, and phosphorous for growth. Corrosion is often blamed on
iron-oxidizing bacteria or SRB. However, these organisms are typically only part of a complex colony of
multiple types of interdependent organisms, each capable of creating by-products that might be a food source
for others.

e) In-leakage of process contaminants such as hydrocarbons or H2S may lead to a massive increase in
biofouling and corrosion.

3.45.4 Affected Units or Equipment

a) MIC is often found in water-cooled heat exchangers, in the bottom water layer of storage tanks, in piping with
stagnant or low flow, and in piping in contact with some soils.

Product storage tanks and water-cooled heat exchangers in any unit where cooling water is not properly
treated can be affected.

Stagnant process lines with trapped water can suffer from MIC.

b) Drain systems and other water-containing systems associated with docks and ship loading/unloading
facilities can experience MIC.

c) MIC is commonly found in equipment where the hydrotest water has not been removed or where equipment
has been left outside and unprotected. 300 series SS are often affected unless precautionary measures are
taken.

d) Fire-water systems can be affected.

 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 239

3.45.5 Appearance or Morphology of Damage MIC corrosion is usually observed as___________.

Answer: localized pitting under deposits or tubercles that shield the organisms.

a) MIC corrosion is frequently observed as localized pitting under deposits or tubercles that shield the
organisms. Tubercles also form on carbon steel exposed to oxygenated water, so the presence of tubercles
is not a guarantee of MIC.

b) Damage is often characterized by cup-shaped pits within pits (the halo effect) in carbon steel or subsurface
cavities in stainless steel. (Figure 3-45-1 to Figure 3-45-7) However, these pits are often indistinguishable
from under-deposit corrosion in carbon steel and chloride pitting in stainless steels. Pit morphology alone
may not be a reliable indicator of the cause of corrosion.

3.45.6 Prevention/Mitigation

a) Microbes require water to thrive. Systems that contain water (cooling water, storage tanks, etc.) should be
treated with biocides such as chlorine, bromine, ozone, ultraviolet light, or proprietary compounds. Often,
multiple biocides are needed to keep the levels of bacteria in the appropriate ranges.

b) Proper application of biocides will control, but not eliminate, microbes; therefore, continued treatment is often
necessary.

c) Periodically flushing and cleaning susceptible systems will help minimize colony growth and resultant MIC.

d) Minimize low-flow or stagnant zones in water-containing systems. A flow rate of 3 fps (1 m/s) will inhibit colony
formation and thereby minimize the likelihood of MIC.

e) Lines should be sloped to assist in drainage.

f) Systems that are not designed or intended for water containment should be kept clean and dry.

g) Empty hydrotest water as soon as possible. Remove moisture and prevent additional moisture intrusion.

h) Coating and cathodically protecting underground structures and interiors of storage tanks have been shown
to be effective mitigation methods for MIC.

i) Biocides are generally not effective in a system that is already contaminated with colonies protected by a
sludge layer. Effective mitigation of established organisms requires complete removal of deposits and
organisms, typically using some combination of pigging, blasting, chemical cleaning, and biocide treatment.

3.45.7 Inspection and Monitoring

a) In cooling water systems, effectiveness of treatment is monitored by measuring biocide residual, microbe
counts, and visual appearance of the water. Sampling and analysis can be performed to better understand
the bacteria population (e.g. ATP, qPCR). While effective treatment and monitoring are key to identifying the
potential for MIC, it still can occur in areas with stagnant flow. Also, the type of microorganisms being
investigated should be identified to ensure proper incubation of water samples (e.g. using an appropriate
temperature for incubation for thermophilic bacteria).

b) Special probes have been designed to monitor for evidence of fouling that may precede or coincide with MIC
damage. Corrosion coupons can be used to identify MIC by sampling the coupon surface after it is pulled
from service; however, it should be noted that just because sessile bacteria populations are not found on the
coupon, it does not mean they do not exist in the system.

c) An increase in the loss of duty of a heat exchanger may be indicative of fouling and potential MIC damage.
RFT can be performed to gauge depth of corrosion on heat exchanger tubes.

d) Foul smelling water may indicate biological activity.

240 API RECOMMENDED PRACTICE 571

e) MIC is often highly localized, so a technique that can find localized corrosion should be chosen, as applicable
to the circumstances (e.g. VT, AUT, or RT).

3.45.8 Related Mechanisms

Cooling water corrosion (3.20), brine corrosion (3.10), oxygenated water corrosion (3.49), and concentration cell
corrosion (3.19).

Figure 3-45-1—MIC on a diesel tank bottom.

 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 241

Figure 3-45-2—Pitting corrosion on the ID of a 6-in. carbon steel sour crude line after 2½ years of
service. Pits are approximately 1-in. to 2-in. wide. Note the halo effect in Figure 3-43-3.

Figure 3-45-3—Same pipe as Figure 3-43-2. Note the halo effect.

242 API RECOMMENDED PRACTICE 571

Figure 3-45-4—Oil line with MIC damage beneath tubercles.

Figure 3-45-5—Same oil line as Figure 3-43-4. Hemispherical pitting typical

of MIC can be seen after grit blasting to remove the scale.
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 243

Figure 3-45-6—Type 304 stainless steel exchanger tubes failed from pitting corrosion on
the shell side in cooling water service after 2½ years without biocide treatment.

Figure 3-45-7—A cross section of the tube in Figure 3-43-6 revealing

severe subsurface tunneling, typical of MIC.
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 293

3.57 Soil Corrosion

3.57.1 Description of Damage

The corrosion of metals from exposure to soils is referred to as soil corrosion.

3.57.2 Affected Materials

Carbon steel, cast iron, and ductile iron.

3.57.3 Critical Factors

a) The severity of soil corrosion is determined by many factors, including operating temperature, moisture and
oxygen availability, soil resistivity (soil condition and characteristics), soil type (water drainage capability) and
homogeneity (variation in soil type), cathodic protection, stray current drainage, and coating type, age, and
condition.

b) There is no single parameter that can be used to determine soil corrosivity. Instead, a number of
characteristics must be combined to estimate the corrosion in particular soil as outlined in ASTM STP 741
as well as API 580 and API 581.

c) Soil resistivity is related to the soil moisture content and dissolved electrolytes in the soil water. Soil resistivity
testing is frequently used to estimate soil corrosivity, mainly because it is easy to measure; however, it can
produce widely variable results within a single refinery site.

d) Soils having high moisture content, high dissolved salt concentrations, and high acidity are usually the most
corrosive.

e) Soil-to-air interface areas are often much more susceptible to corrosion than the rest of the structure because
of moisture and oxygen availability. (Figure 3-57-1)

f) Corrosion rates increase with increasing metal temperature.

g) Other factors that affect soil corrosion include galvanic corrosion, dissimilar soils, stray currents, differential
aeration corrosion cells, and MIC.

3.57.4 Affected Units or Equipment

a) Underground piping and equipment as well as buried tanks and the bottoms of aboveground storage tanks.
(Figure 3-57-2)

b) Ground supported metal structures. (Figure 3-57-2)

c) Piping running close to the ground under which soil has accumulated over the years to the point of reaching
and contacting or partially covering the pipe.

d) Piping exiting road or other crossings where soil has sloughed off and is laying on or covering the pipe.

3.57.5 Appearance or Morphology of Damage

a) Soil corrosion appears as external thinning with a roughened surface and localized deeper attack or pitting.

b) Poor condition of a protective coating is a tell-tale sign of potential corrosion damage.

c) Soil corrosion can be highly variable along an unprotected buried pipe or on the unprotected underside of a
storage tank bottom. (Figure 3-57-3)
294 API RECOMMENDED PRACTICE 571

3.57.6 Prevention/Mitigation

Soil corrosion of carbon steel can be minimized through the use of appropriate coatings and cathodic protection
along with special backfill to prevent rock damage to the coating. The most effective protection is a combination
of a corrosion-resistant coating and a cathodic protection system.

3.57.7 Inspection and Monitoring

The following techniques can be used for inspecting buried or on-grade metallic components that may have
become covered by shifting soil, as well as soil-to-air interfaces.

a) An aboveground visual survey can identify leaks coming to the surface of the soil.

NOTE Any change in the surface contour of the ground, discoloration of the soil, softening of paving asphalt, pool
formation, bubbling water puddles, or noticeable odor.

b) Smart-pigging devices employing UT or MFL can be used where the piping is designed to send and receive
the pigs or accommodate tethered pigs that can be sent through lines. It can detect dents, flaws, and
corrosion.

c) A close-interval potential survey on a cathodically protected line may be used to verify that the buried piping
has a protective potential throughout its length. API 570 provides guidance for conducting close-interval
surveys. Close-interval potential surveys can only infer wall loss from CP potential, but not directly detect
presence of wall loss, and thus they identify areas for follow-up inspection. Refer to NACE SP0169 and
API 651 Section 11 of for guidance applicable to inspecting and maintaining cathodic protection systems for
buried and soil-contacting equipment.

d) A pipe coating holiday survey (e.g. direct current voltage gradient) can be used to locate coating defects on
coated pipes. This can be performed on newly coated pipe before being buried or on pipe that has been
excavated.

e) VT of the pipe or equipment coating after excavation is one of the most reliable methods to determine its
condition. This is also commonly done at the soil-to-air interface, where the soil should be removed down to
about 12 in. (305 mm) below the surface to expose the most corrosion-prone area. Care should be taken
during excavation to avoid damaging the coating or the equipment. Risks of excavating pipe while in service
should be evaluated.

f) GWT can provide a screening tool for metal loss on buried piping, but signal loss can limit the distance from
the GWT collar over which the piping can be inspected.

g) Pressure testing can determine whether buried equipment is leaking at that particular time but does not
provide information concerning the degree of corrosion on the equipment.

3.57.8 Related Mechanisms

Galvanic corrosion (3.31), concentration cell corrosion (3.19), graphitic corrosion (3.33), and MIC (3.45).
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 295

Figure 3-57-1—Corrosion of carbon steel pipe at the soil/air

interface where the pipe emerges from underground.
296 API RECOMMENDED PRACTICE 571

Figure 3-57-2—Coupons removed from the bottom of an unprotected steel condensate

storage tank after 3 years of service. The external surface is shown.

Figure 3-57-3—Cross section through location (A) showing severe corrosion.

The arrows point to a location that was at the original thickness.
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 297

3.58 Sour Water Corrosion (Acidic)

3.58.1 Description of Damage

a) Corrosion of steel (primarily) due to acidic sour water (SW) containing H2S at a pH between 4.5 and 7.0.
Carbon dioxide (CO2) may also be present as well as other acidic species such as dissolved organic acids.

b) SWs containing significant amounts of ammonia, chlorides, or cyanides, which may significantly affect pH,
are outside the scope of this section.

3.58.2 Affected Materials

a) Primarily affects carbon steel.

b) Stainless steels, copper alloys, and nickel-based alloys are usually resistant.

3.58.3 Critical Factors

a) H2S content, pH, temperature, velocity, and oxygen concentration are all critical factors.

b) The H2S concentration in the SW is dependent on the H2S partial pressure in the gas phase as well as
temperature and pH.

c) At a given pressure, the H2S concentration in the SW decreases as temperature increases.

d) Increasing concentrations of H2S tend to decrease solution pH down to about 4.5. Streams with a pH below
4.5 indicate the presence of a strong acid, which would be the main corrosion concern.

e) Above a pH of about 4.5, a protective, thin, iron sulfide layer helps limit the corrosion rate.

f) In some instances, at a pH above 4.5, a thicker, porous sulfide film layer can form. This can promote pitting
under the sulfide deposits.

g) Other contaminants have a significant effect on water pH. For example, HCl and CO2 reduce the pH (make
it more acidic). Ammonia significantly increases pH and is more often associated with alkaline SW where the
main concern is ammonium bisulfide corrosion. (See 3.5.)

h) The presence of air or oxidants may increase the corrosion rate and usually produces pitting or under-deposit
attack.

3.58.4 Affected Units or Equipment

Acidic SW corrosion is a concern in overhead systems of FCC and coker gas fractionation plants with high H2S
levels and low NH3 levels.

3.58.5 Appearance or Morphology of Damage

a) Corrosion damage from acidic SW is typically general thinning. However, localized corrosion or localized
under-deposit attack can occur, especially if air or oxygen is present. (Corrosion in high-CO2 environments
caused primarily by the CO2 is covered in 3.18.)

b) 300 series SS is susceptible to pitting attack and may experience crevice corrosion and/or Cl− SCC. (See
3.17.)
298 API RECOMMENDED PRACTICE 571

3.58.6 Prevention/Mitigation

a) Process monitoring and control are important for minimizing the effects of acidic SW corrosion. Process
parameters that typically should be monitored, e.g. at water draws of overhead accumulators, and controlled
where applicable, are as follows:

H2S content,

pH,

chloride content,

cyanide content,

temperature,

fluid velocity, and

oxygen concentration.

b) 300 series SS can be used at temperatures below about 140 °F (60 °C) where Cl− SCC is not likely.

c) Copper alloys and nickel alloys are generally not susceptible to acid SW corrosion. However, copper alloys
are vulnerable to corrosion and some are susceptible to SCC in environments with ammonia.

d) Water wash injection into FCC overheads and coker light ends units dissolves and dilutes corrodents like
H2S and cyanide (CN−). Additional injection of a polysulfide solution with the water wash helps to convert
cyanides into a less harmful compound.

3.58.7 Inspection and Monitoring

a) UT scanning and RT can identify locally thinned areas of equipment exposed to SW corrosion.

b) Permanently mounted thickness monitoring sensors can be used.

c) Strategically placing continuous corrosion monitoring in the system, e.g. corrosion probes, corrosion
coupons, or online thickness monitoring sensors, can provide an early indication of increased corrosion rates
and the need to conduct thickness surveys or apply more advanced NDE to verify the severity and extent of
the indicated corrosion.

NOTE Corrosion probes may provide misleading data due to formation of FeS scale on the probe.

d) Process monitoring and control, as described in 3.58.6 above, are key to controlling acidic SW corrosion and
helping identify areas that should be included in the inspection plan.

3.58.8 Related Mechanisms

Other damage mechanisms to consider in these environments include wet H2S damage (3.67) and CO2 corrosion
(3.18). See also ammonium bisulfide corrosion (3.5) and concentration cell corrosion (3.19).
300 API RECOMMENDED PRACTICE 571

3.59 Spheroidization (Softening)

3.59.1 Description of Damage

Spheroidization is a change in the microstructure of steels resulting from exposure in the 850 °F to 1400 °F
(440 °C to 760 °C) range, where the carbide phases in carbon steels and C-½Mo steels are unstable and may
agglomerate from their normal plate-like form to a spheroidal form or from small, finely dispersed carbides in Cr-
Mo steels to large agglomerated carbides. Spheroidization may cause a loss in strength and/or creep resistance.

3.59.2 Affected Materials

All commonly used grades of carbon steel and low-alloy steels including C-½Mo, 1Cr-½Mo, 1¼Cr-½Mo, 2¼Cr-
1Mo, 3Cr-1Mo, 5Cr-½Mo, and 9Cr-1Mo steels.

3.59.3 Critical Factors

a) Metal chemical composition, microstructure, exposure time, and temperature are critical factors.

b) The rate of spheroidization depends on the temperature and initial microstructure. Spheroidization can occur
in a few hours at 1300 °F (550 °C) but may take several years at 850 °F (455 °C).

c) Annealed steels are more resistant to spheroidization than normalized steels. Coarse-grained steels are
more resistant than fine grained. Fine-grained silicon-killed steels are more resistant than aluminum killed.

3.59.4 Affected Units or Equipment

a) Spheroidization can occur in piping and equipment after exposure to temperatures above 850 °F (455 °C).
The loss in strength may be as high as about 30 %, but failure is not likely to occur except under very high
applied stresses, in areas of stress concentration, or in combination with other damage mechanisms.

b) The loss in strength is usually accompanied by an increase in ductility, which allows for deformation at stress
concentrations.

c) Spheroidization affects hot-wall piping and equipment in the FCC, catalytic reforming, and coker units. Fired
boiler tubes and fired heater tubes in process units may be affected by a loss in creep strength, but equipment
is seldom renewed or repaired because of spheroidization.

3.59.5 Appearance or Morphology of Damage

a) Spheroidization is not visible or readily apparent and can only be observed through metallography. In carbon
steel, the pearlite phase undergoes a time-dependent transformation from partial to complete
spheroidization. (Figure 3-59-1 and Figure 3-59-2)

b) In the case of the 5 % to 9 % Cr-Mo alloys, spheroidization is the process of transforming the carbides from
their original finely dispersed morphology to large agglomerated carbides.

3.59.6 Prevention/Mitigation

Spheroidization is difficult to prevent except by minimizing long-term exposure to elevated temperatures.

3.59.7 Inspection and Monitoring

a) Spheroidization is primarily found using FMR or removal of samples for metallographic evaluation.

b) Because spheroidization may result in a reduction in tensile strength (and therefore, hardness), field
hardness testing may indicate the presence of spheroidization, but it should be followed up with sampling
and/or FMR to confirm its existence.
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 301

3.59.8 Related Mechanisms

Closely related to graphitization (3.34). Spheroidization and graphitization are competing mechanisms that occur
at overlapping temperature ranges. At temperatures above about 1025 °F (550 °C), graphitization may occur
after spheroidization. Below 1025 °F (550 °C), graphitization occurs before the steel is fully spheroidized.
302 API RECOMMENDED PRACTICE 571

Figure 3-59-1—High-magnification photomicrograph of metallographic sample

showing typical ferrite-pearlite structure of carbon steel.

Figure 3-59-2—High-magnification photomicrograph of

metallographic sample showing spheroidized carbides.
312 API RECOMMENDED PRACTICE 571

3.62 Sulfuric Acid Corrosion

3.62.1 Description of Damage

Sulfuric acid promotes general and localized corrosion of carbon steel and other alloys. Carbon steel HAZs may
experience accelerated corrosion.

3.62.2 Affected Materials

In order of increasing resistance: carbon steel, 316L SS, Alloy 20, high-silicon cast iron, high-nickel cast iron,
Alloy B-2, and Alloy C-276. Hastelloy

3.62.3 Critical Factors

a) Acid concentration, temperature, alloy content, velocity, contamination, and presence of oxidizers.

b) Figure 3-62-1 shows a plot of carbon steel corrosion rates as a function of sulfuric acid concentration and
temperature.

c) Corrosion of steel by dilute acid is usually in the form of overall metal loss or pitting and becomes more
severe with increasing temperature and velocity.

d) Carbon steel corrosion rates increase significantly if the flow velocity exceeds about 2 fps to 3 fps (0.6 m/s
to 0.9 m/s) or at acid concentrations below 65 %, since these conditions reduce the ability to maintain a
protective ferrous sulfate scale.

e) Under stagnant or low-flow conditions [<0.5 fps (<0.15 m/s)], a mechanism known as hydrogen grooving can
occur where movement of hydrogen bubbles on the steel surface removes the protective film and locally
increases the corrosion rate. It is essentially an erosion-corrosion mechanism. Hydrogen grooving can cause
corrosion along the sides and top of piping and equipment.

f) Mix points where acid is mixed with neutral or alkaline water cause heat to be released, with the resulting
elevated temperature causing an acceleration of the corrosion rate. High corrosion rates can also occur
where concentrated acid becomes diluted.

g) The presence of oxidizers (e.g. oxygen) or contaminants (e.g. iron) can greatly increase the corrosion rate,
especially for Alloy B-2.

h) Stainless steel performance can be similar to carbon steel, especially in <92 % H2SO4 or at elevated
temperatures. The addition of Mo to 300 series SS can improve corrosion resistance in <92 % H2SO4, but
performance is still unpredictable due to the ability of the acid to act as either a reducing acid or an oxidizing
acid depending on concentration and contaminants.

3.62.4 Affected Units or Equipment

a) Sulfuric acid alkylation units and waste water treatment plants are affected.

b) Areas of vulnerability in sulfuric acid alkylation units include contactors, reactor effluent lines, reboilers,
deisobutanizer overhead systems, and the caustic treating section. (Figure 3-62-2 and Figure 3-62-3)

c) Acid and acid esters can carry over from the treating section and get into the distillation section. Acid
concentrates in the reboilers and boils into the overhead. Similarly, acid esters can thermally decompose in
the distillation section reboilers to form sulfurous or sulfuric acid, both of which vaporize and travel to the
overhead.

d) Rivulet corrosion can occur in tanks and vessels where dilute acid refluxes down the sides of the tank or
vessel. This condition can also occur at the air to liquid interface or rag layer.
 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 313

e) Hydrogen grooving can occur in low-flow or stagnant areas such as in storage tanks, rail cars, or dead-legs.

f) Vessels handling sulfuric acid can be severely corroded when cleaning the vessel for internal inspection.
Mixing concentrated sulfuric acid with cleaning water (which will also release a lot of heat and energy) will
form dilute, highly corrosive acid that can cause a lot of damage in short period of time.

3.62.5 Appearance or Morphology of Damage

a) Attack can be localized or general depending upon acid concentration, flow velocity, and the location of
vapor/liquid interface areas.

Localized corrosion can occur in piping or other areas with high flow.

Carbon steel weld HAZs can be attacked rapidly.

Rivulet corrosion, hydrogen grooving, and corrosion at the vapor/liquid or air/liquid interface are localized.

b) Localized corrosion can be so uniform that VT may not notice the transition from shallow to deep metal loss.

c) “Knife-line” grooving is typical at tops of horizontal piping where hydrogen bubbles form and travel along the
top of the pipe. Areas of “fan”-shaped or “delta”-shaped corrosion are common at elbows.

d) Sulfuric acid attacks slag left from welding.

e) If the corrosion rate and velocity are high, there will be no scale.

3.62.6 Prevention/Mitigation

a) Corrosion is minimized through proper materials selection and proper operation within design velocities.

b) Alloys such as Alloy 20, Alloy 904L, and Alloy C-276 resist dilute acid corrosion and form a protective iron
sulfate film on the surface.

c) Acidified product streams can be washed with caustic to neutralize the acid.

d) Because the cleaning of vessels containing concentrated H2SO4 can cause serious corrosion [see 3.62.4 f)],
when carbon steel (or other non-resistant material) vessels must be emptied, a neutralization procedure that
is safe and mitigates corrosion should be followed.

3.62.7 Inspection and Monitoring

a) Localized corrosion due to sulfuric acid can be detected and measured by UT and RT.

b) Permanently mounted thickness monitoring sensors can be used.

c) Corrosion can be monitored with coupons and ER probes.

d) To avoid potential corrosion from clean-out of vessels containing concentrated H2SO4, they should be
considered for non-intrusive inspection. When clean-out is performed, inspection should be considered after
clean-out to ensure no significant damage resulted from the cleaning process.

3.62.8 Related Mechanisms

None.
314 API RECOMMENDED PRACTICE 571

What is the Sulfuric acid corrosion rate if the Sulfuric acid 85% and Temperature 125 ºF?

Figure 3-62-1—Sulfuric acid corrosion rate chart for carbon steel.

 DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 315

Figure 3-62-2—Accelerated sulfuric acid corrosion under a baffle.

Figure 3-62-3—Grooving corrosion in the carbon steel vapor line from an

alkaline water wash drum in a sulfuric acid alkylation unit.