Self-Study on API RP 571

Damage Mechanisms Affecting Fixed Equipment in the Refining

Industry
First Ed, Dec 2003

Oli Ismail

Internal
 TOC
• 1.0 – Intro & Scope
• 2.0 – References
• 3.0 – Definition of Terms & Abbreviations
• 4.0 – General Damage Mechanisms – All Industries
– General
– Mechanical & metallurgical failure mechanisms
– Uniform or localized loss of thickness
– High temp corrosion (204 C [400 F])
– Environment-assisted cracking
• 5.0 – Refining Industry Damage Mechanisms
– General
– Process Unit PFD’s

Internal
 1.1 Intro
• ASME and API codes do not address
equipment deterioration
• 1st step in Fitness-For-Service (FFS) assessment
per API RP 579 is to identify flaw type and
cause of damage
• Also, 1st step in Risk-Based Inspection (RBI) per
API RP 580 is to identify damage mechanisms
properly

Internal
 1.1 Intro
• In FFS or RBI, it is important to know cause of damage observed or anticipated, and
likelihood and degree of further damage in future
• The causes varies:-
– Pre-existing conditions before service
– Service-induced
– Inadequate design (material selection & design details)
– Interaction with aggressive environments / conditions during normal service or transient periods
• Factor that complicates FFS or RBI :- “material / environmental condition interactions
are extremely varied”
• In general, the following types of damages in petrochemical equipment:-
– General and local metal loss due to corrosion and/or erosion
– Surface connected cracking
– Subsurface cracking
– Microfissuring/microvoid formation
– Metallurgical changes

Internal
 1.2 Scope
• General guidance as to the most likely damage mechanisms
in refining and petrochemical industry is provided in the
recommended practice (RP)
• The guideline provide info on likely causes of damage, and to
introduce concepts of service-induced deterioration and
failure modes
• The summary provided for each damage mechanism
provides the fundamental information required for a FFS
assessment per API RP 579 or an RBI study per API RP 580
• The descriptions are not definitive guideline for every
possible situation

Internal
 1.3 Organization & Use
The information for each damage mechanism is provided in a set format as shown below. This recommended practice format facilitates
use of the information in the development of inspection programs, FFS assessment and RBI applications.
a) Description of Damage – a basic description of the damage mechanism.
b) Affected Materials – a list of the materials prone to the damage mechanism.
c) Critical Factors – a list of factors that affect the damage mechanism (i.e. rate of damage).
d) Affected Units or Equipment – a list of the affected equipment and/or units where the damage mechanism commonly occurs is
provided. This information is also shown on process flow diagrams for typical process units.
e) Appearance or Morphology of Damage – a description of the damage mechanism, with pictures in some cases, to assist with
recognition of the damage.
f) Prevention / Mitigation – methods to prevent and/or mitigate damage.
g) Inspection and Monitoring – recommendations for NDE for detecting and sizing the flaw types associated with the damage
mechanism.
h) Related Mechanisms – a discussion of related damage mechanisms.
i) References – a list of references that provide background and other pertinent information.

• Common damage mechanisms covered in Section 4.0

• Specific damage mechanisms for refining and petrochemical industry covered in Section 5.0

• Section 5.2 provides process flow diagrams, in determining primary locations where commonly found

Metal loss, pitting, creep

Internal
 1.4 References
2.1 Standards
The following standards, codes and specifications are cited in the recommended practice. Unless otherwisespecified, the most recent editions of these documents shall apply.
API
• API 530 Pressure Vessel Inspection Code
• Std. 530 Calculation of Heater Tube Thickness in Petroleum Refineries
• RP 579 Fitness-For-Service
• Publ. 581 Risk-Based Inspection - Base Resource Document
• Std. 660 Shell and Tube Heat Exchangers for General Refinery Service
• RP 751 Safe Operation of Hydrofluoric Acid Alkylation Units
• RP 932-B Design, Materials, Fabrication, Operation and Inspection Guidelines for Corrosion Control in Hydroprocessing Reactor Effluent Air Cooler (REAC) Systems
• RP 934 Materials and Fabrication Requirements for 2-1/4 Cr-1Mo & 3Cr-1Mo Steel Heavy Wall Pressure Vessels for High Temperature, High Pressure Service
• RP 941 Steels for Hydrogen Service at Elevated Temperatures and Pressures in Petroleum Refineries and Petrochemical Plants
• RP 945 Avoiding Environmental Cracking in Amine Units

ASM1
• Metals Handbook Volume 1, Properties and Selection: Iron, Steels, and High-Performance Alloys;
• Volume 13, Corrosion in Petroleum Refining and Petrochemical Operations;
• Volume 11, Failure Analysis and Prevention

ASME2
• Boiler and Pressure Vessel Code Section III, Division I, Rules for Construction of Nuclear Power Plant Components; Section VIII, Division I, Pressure Vessels.

ASTM3
• MNL41 Corrosion in the Petrochemical Industry
• STP1428 Thermo-mechanical Fatigue Behavior of Materials

BSI4
• BSI 7910 Guidance on Methods for Assessing the Acceptability of Flaws in Fusion Welded Structures

MPC5
• Report FS-26 Fitness-For Service Evaluation Procedures for Operating Pressure Vessels, Tanks and Piping in Refinery and Chemical Service

Internal
 1.4 References
NACE6
• Std. MR 0103 Materials Resistant to Sulfide Stress Cracking in Corrosive Petroleum Refining Environments”
• RP 0169 Standard Recommended Practice: Control of External Corrosion on Underground or Submerged Metallic Piping Systems
• RP 0170 Protection of Austenitic Stainless Steels and Other Austenitic Alloys from Polythionic Acid Stress Corrosion Cracking during
Shutdown of Refinery Equipment
• RP 0198 The Control of Corrosion Under Thermal Insulation, and Fireproofing – A Systems Approach
• RP 0294 Design, Fabrication, and Inspection of Tanks for the Storage of Concentrated Sulfuric Acid and Oleum at Ambient Temperatures
• RP 0296 Guidelines for Detection, Repair and Mitigation of Cracking of Existing Petroleum Refinery Pressure Vessels in Wet H2S
Environments
• RP 0472 Methods and Controls to Prevent in-Service Environmental Cracking of Carbon Steel Weldments in Corrosive Petroleum Refining
Environments
• Publ. 5A151 Materials of Construction for Handling Sulfuric Acid
• Publ. 5A171 Materials for Receiving, Handling, and Storing Hydrofluoric Acid
• Publ. 8X194 Materials and Fabrication Practices for New Pressure Vessels used in Wet H2S Refinery Service

WRC7
• Bulletin 275 The Use of Quenched and Tempered 2-1/4Cr-1Mo Steel for Thick Wall Reactor Vessels in Petroleum Refinery Processes: An
Interpretive Review of 25 Years of Research and Application

2.2 Other References

A list of publications that offer background and other information pertinent to the damage mechanism is provided in the section covering
each damage mechanism.

Internal
 3.1 Terms
3.1.1 Austenitic – a term that refers to a type of metallurgical structure (austenite) normally found in 300 Series
stainless steels and nickel base alloys.
3.1.2 Austenitic stainless steels – the 300 Series stainless steels including Types 304, 304L, 304H, 309, 310, 316, 316L,
316H, 321, 321H, 347, and 347H. The “L” and “H” suffixes refer to controlled ranges of low and high carbon content,
respectively. These alloys are characterized by an austenitic structure.
3.1.3 Carbon steel – steels that do not have alloying elements intentionally added. However, there may be small
amounts of elements permitted by specifications such as SA516 and SA106, for example that can affect corrosion
resistance, hardness after welding, and toughness. Elements which may be found in small quantities include Cr, Ni, Mo,
Cu, S, Si, P, Al, V and B.
3.1.4 Diethanolamine (DEA) – used in amine treating to remove H2S and CO2 from hydrocarbon streams.
3.1.5 Duplex stainless steel – a family of stainless steels that contain a mixed austenitic-ferritic structure including Alloy
2205, 2304, and 2507. The welds of 300 series stainless steels may also exhibit a duplex structure.
3.1.6 Ferritic – a term that refers to a type of metallurgical structure (ferrite) normally found in carbon and low alloy
steels and many 400 series stainless steels.
3.1.7 Ferritic stainless steels – include Types 405, 409, 430, 442, and 446.
3.1.8 Heat Affected Zone (HAZ) – the portion of the base metal adjacent to a weld which has not been melted, but
whose metallurgical microstructure and mechanical properties have been changed by the heat of welding, sometimes
with undesirable effects.
3.1.9 Hydrogen Induced Cracking (HIC) – describes stepwise internal cracks that connect adjacent hydrogen blisters on
different planes in the metal, or to the metal surface. No externally applied stress is needed for the formation of HIC.
The development of internal cracks (sometimes referred to as blister cracks) tends to link with other cracks by a
transgranular plastic shear mechanism because of internal pressure resulting from the accumulation of hydrogen. The
link-up of these cracks on different planes in steels has been referred to as stepwise cracking to characterize the nature
of the crack appearance.
Internal
 3.1 Terms
3.1.10 Low alloy steel – a family of steels containing up to 9% chromium and other alloying additions for high
temperature strength and creep resistance. The materials include C-0.5Mo, Mn-0.5Mo, 1Cr-0.5Mo, 1.25 Cr-0.5Mo,
2.25Cr-1.0Mo, 5Cr-0.5Mo, and 9Cr-1Mo. These are considered ferritic steels.
3.1.11 Martensitic – a term that refers to a type of metallurgical structure (martensite) normally found in some 400
series stainless steel. Heat treatment and or welding followed by rapid cooling can produce this structure in carbon and
low alloy steels.
3.1.12 Martensitic stainless steel – include Types 410, 410S, 416, 420, 440A, 440B, and 440C.
3.1.13 Methyldiethanolamine (MDEA) – used in amine treating to remove H2S and CO2 from hydrocarbon streams.
3.1.14 Monoethanolamine (MEA) – used in amine treating to remove H2S and CO2 from hydrocarbon streams.
3.1.15 Nickel base – a family of alloys containing nickel as a major alloying element (>30%) including Alloys 200, 400, K-
500, 800, 800H, 825, 600, 600H, 617, 625, 718, X-750, and C276.
3.1.16 Stress oriented hydrogen induced cracking (SOHIC) – describes an array of cracks, aligned nearly perpendicular to
the stress, that are formed by the link-up of small HIC cracks in steel. Tensile strength (residual or applied) is required to
produce SOHIC. SOHIC is commonly observed in the base metal adjacent to the Heat Affected Zone (HAZ) of a weld,
oriented in the through-thickness direction. SOHIC may also be produced in susceptible steels at other high stress points,
such as from the tip of the mechanical cracks and defects, or from the interaction among HIC on different planes in the
steel.
3.1.17 Stainless steel – there are four categories of stainless steels that are characterized by their metallurgical structure
at room temperature: austenitic, ferritic, martensitic and duplex. These alloys have varying amounts of chromium and
other alloying elements that give them resistance to oxidation, sulfidation and other forms of corrosion depending on
the alloy content.

Internal
 • Galvanic Corrosion
• Graphitization
• Softening (Spheroidization)
• Atmospheric Corrosion
• Temper Embrittlement • Corrosion Under
• Strain Aging Insulation (CUI)
• 475C Embrittlement
• Sigma Phase Embrittlement
• Cooling Water Corrosion
• Brittle Fracture • Boiler Water Condensate
• Creep and Stress Rupture Corrosion
• Thermal Fatigue
• Short Term Overheating – Stress Rupture
• CO2 Corrosion
• Steam Blanketing • Fuel-Gas Dew-Point
• Dissimilar Weld Cracking Corrosion
• Thermal Shock
• Erosion / Erosion – Corrosion
• Microbiologically Induced
• Cavitation Uniform or Corrosion (MIC)
• Mechanical Fatigue Mechanical & Localized Loss • Soil Corrosion
• Vibration-Induced Fatigue Metallurgical of Thickness
• Refractory Degradation • Caustic Corrosion
Failure
• Reheat Cracking • Deallloying
• Graphitic Corrosion

Environment-
High
Assisted
Temperature
Cracking
Corrosion
(204C)
• Chloride Stress Corrosion Cracking • Oxidation
• Corrosion Fatigue
• Caustic Stress Corrosion Cracking (Caustic Embrittlement)
• Sulfidation
• Ammonia Stress Corrosion Cracking • Carburization
• Liquid Metal Embrittlement (LME) • Decarburization
• Hydrogen Embrittlement (HE)
• Metal Dusting
• Fuel Ash Corrosion
• Nitriding
Internal
 Mechanical & Metallurgical Failure Mechanism

Internal
 Mechanical & Metallurgical Failure Mechanism

Graphitization
Description • Change in microstructure
of damage • After long-term operation in 427 – 593 degC
• May cause loss of strength, ductility, and/or creep resistance

Affected • Some grades of CS

materials • 0.5Mo steels
• Low alloy C-Mo steels with up to 1% Mo.

Critical
factors

Affected • Hot wall piping and equipment in FCC, catalytic reforming and coker units
units / • Bainitic grades are less susceptible than coarse pearlitic grades
equipment

Appearance • Not visible

or • Require metallographic examination
morphology • Advanced stages of damage related to loss in creep strength may include microfissuring / microvoid formation, subsurface cracking and
of damage surface connected cracking

Prevention / • Add 0.7% chromium for long term operation above 427degC
Mitigation

Inspection & • Metallographic examination

monitoring • Advanced stages of damage related to loss in strength include surface breaking cracks or creep deformation that may be difficult to detect

Related • Spheroidization tends to occur above 551degC, while graphitization predominates below this temp
mechanisms
Internal
Internal
 Mechanical & Metallurgical Failure Mechanism

Spheroidization (Softening)
Description • Change in microstructure
of damage • After exposurein 440 – 760 degC
• May cause loss of strength and/or creep resistance

Affected • All commonly used grades of CS and low alloy steels • 2.25Cr-1Mo
materials • C-0.5Mo • 3Cr-1Mo
• 1Cr-0.5Mo • 5Cr-0.5Mo
• 1.25Cr-0.5Mo • 9Cr-1Mo

Critical • Metal chemistry

factors • Microstructure
• Exposure time
• Temperature

Affected • Piping and equipment after exposure to temps above 454degC

units / • Hot wall piping and equipment in FCC, catalytic reforming and coker units
equipment • Fired heater tubes in boilers or process units may be affected by loss in creep strength
• Equipment, in general, is seldom renewed or repaired due to spheroidization

Appearance • Not visible

or • Require metallography. The pearlitic phase undergoes time dependant transformation from partial to complete spheroidization.
morphology • For 5% to 9% CrMo alloys, spheroidization is the process of transforming carbides from originally finely dispersed to large agglomerated
of damage (chunks) carbides

Prevention / • Minimize long-term exposure to elevated temperatures

Mitigation

Inspection & • Field metallography or removal of samples for metallographic observation

monitoring • Spheroidized microstructure might incur reduced tensile strength and/or hardness

Related • Spheroidization tends to occur above 551degC, while graphitization predominates below this temp
mechanisms • Below 552degC graphitization occurs before the steel is fully spheroidized
Internal
Internal
 Mechanical & Metallurgical Failure Mechanism

Temper Embrittlement
Description • Reduction in toughness
of damage • Metallurgical change in some low alloy steels
• Result of long term exposure in the 343 – 593degC
• Causes upward shift in ductile-to-brittle transition temp (measured by Charpy impact test)
• Loss of toughness not evident during operation; may be susceptible to brittle fracture failure during start-up and shutdown
Affected • Primarily 2.25Cr-1Mo low alloy steel • Older generation 2.25Cr-1Mo , mfc prior to 1972
materials • 3Cr-1Mo • 5Cr-0.5Mo
• High-strength low alloy Cr-Mo-V rotor steels • 9Cr-1Mo

Critical • Alloy steel composition • Presence of manganese, silicon, phosphorus, tin, antimony, arsenic
factors • Thermal history • Hugely reduced structural integrity for parts containing crack-like flaw
• Metal temp • May require material toughness evaluation
• Exposure time

Affected • A variety of process units after long-term exposure to temperatures above 343degC
units / • Most often found in in hydroprocessing units – reactors, hot feed / effluent exchanger components, and hot HP separators
equipment • Catalytic reforming units (reactors and exchangers), FCC reactors, coker, and visbreaking units
• Welds are often more susceptible than the base metal

Morphology • Not readily apparent, can be confirmed by impact test

of damage • May cause catastrophic brittle fracture
• Upward shift in ductile-to-brittle transition temp measured in Charpy V-notch impact test
Prevention / • Existing materials
Mitigation • Use pressurization sequence to limit system pressure to approx 25% of may design pressure for temps below a Minimum
Pressurization Temperature (MPT).
• MPT’s range from 171degC for the most highly temper embrittled steels, down to 38degC or lower for temper embrittlement
resistant steels (as required to also minimize effects of hydrogen embrittlement)
• If weld repairs are required, the effects can be temporarily reversed by heating at 620degC for 2 hours per inch of thickness, and
rapidly cooling to room temp.

• New materials
• Limit levels of manganese, silicon, phosphorus, tin, antimony, and arsenic in base metal and welding consumables.
• Limit “J” factor for base metal and “X” factor for weld metal
• J*= (Si + Mn) x (P + Sn) x 10exp4 {elements in wt%}
• X = (10P +5Sb +4Sn + As)/100 {elements in ppm}
• Typical J* and X factors used for 2.25Cr steel are 100 and 15, respectively.
• Limit the (P + Sn) to less than 0.01%

Internal
 Mechanical & Metallurgical Failure Mechanism

Temper Embrittlement
Inspection & • Field metallography or removal of samples for metallographic observation
monitoring • Spheroidized microstructure might incur reduced tensile strength and/or hardness

Related • Spheroidization tends to occur above 551degC, while graphitization predominates below this temp
mechanisms • Below 552degC graphitization occurs before the steel is fully spheroidized

Internal
Internal
 Mechanical & Metallurgical Failure Mechanism

Strain Aging
Description • Combined effect of deformation and aging at an intermediate temperature
of damage • Results in increase in hardness and strength, with a reduction in ductility and toughness

Affected • Mostly older (pre-1980’s) CS with large grain size

materials • C-0.5Mo low alloy steel
Critical • Steel composition
factors • Mfg process
• Steels manufactured by Bessemer or open hearth process contain higher levels of criticality impurity elements
• In general, steels made by Basic Oxygen Furnace (BOF) and fully killed with aluminium will not be susceptible
• Damage observed in materials that have been cold-worked and in service at intermediate temperatures without stress relieving
• Major concern for equipment with cracks
• Pressurization sequence vs temperature is critical issue to prevent brittle fracture of susceptible materials
• Damage can occur when welding near cracks and notches in a susceptible material
Affected • Wall vessels manufactured from susceptible materials that have not been stress relieved
units /
equipment

Appearance • Formation of brittle cracks that are found through detailed metallurgical analyses
or • But, damage most likely will not be identified as strain aging until fracture has already occurred
morphology
of damage

Prevention / • Avoid stressing or pressurizing equipment until metal temp reaches acceptable level where the risk of brittle fracture is low (refer to curve
Mitigation “A” in UCS 66 of the ASME Code Section VIII, Div 1, for pressurization temps of vessels susceptible to strain aging effects
• Apply PWHT to weld repairs. Where PWHT is not possible, buttering should be considered to minimize welding on old material under
restraint.

Inspection & • Not used to control strain aging

monitoring

Related • When deformation occurs at intermediate temp, the mechanism is referred to as dynamic strain aging
mechanisms • Blue brittleness is another form of strain aging

Internal
 Mechanical & Metallurgical Failure Mechanism

885F (475degC) Embrittlement

Description • Loss in toughness • Exposure to temp range 316 to 540 degC
of damage • Metallurgical change
• Occur in alloys containing ferrite phase

Affected • 400 Series SS (eg. 405, 409, 410, 410S, 430, 446) • Wrought and cast 300 Series SS containing ferrite, particularly
materials • Duplex SS such as alloys 2205, 2304, 2507 welds and weld overlay

Critical • Alloy composition, particularly chromium content • Often assumed that susceptible materials exposed to 371 to
factors • Amount of ferrite phase – increase of phase in high temp 538degC are affected
• Operating temp • Effect of toughness is significant at lower temp during shutdown,
• Operating time at critical temp startups or upsets
• Embrittlement can result from tempering at higher temps or by
holding within of cooling through the transformation range
Affected • Susceptible alloys exposed to embrittling temp range
units / • Most refining companies limit the use of ferritic SS to non-pressure boundary applications because of this damage
equipment • Eg: fractionator trays and internals used in FCC, crude, vacuum & coker units
• Duplex SS heat exchanger tubes & other exposed to temps above 316degC for extended time periods

Appearance • Not readily apparent with metallography

or • Can be confirmed through bend or and impact test
morphology • Existence of damage can be identified in hardness in affected areas. Failure during bend test or impact test of samples removed from
of damage services is the most positive indicator

Prevention / • Use low ferrite or non-ferritic alloys

Mitigation • Avoid exposing susceptible material to the embrittling range
• Possible to minimize effect via modifying chemical composition, but very expensive
• Reversible by heat treatment to dissolve precipitates, followed by rapid cooling; de-embrittling heat treatment temp (typ. 593degC or
higher. (Note: if the de-embrittled component is exposed to the same service conditions, it will re-embrittle faster.
Inspection & • Impact or bend testing of samples removed from services
monitoring • Cracking during turnarounds, or during startup or shutdown when the material is below 93degC and the effects of embrittlement are most
detrimental
• Increase in hardness
Related • NA
mechanisms

Internal
 Mechanical & Metallurgical Failure Mechanism

Sigma Phase Embrittlement

Description • Formation of metallurgical phase known as sigma phase
of damage • Can result in loss of fracture toughness in some SS
• A result of high temp exposure

Affected • 300 Series SS wrought metals, weld metal and castings • 400 Series SS and other ferritic & martensitic SS with 17% Cr or
materials • Cast 300 Series SS including HK & HP alloys are susceptible to more are susceptible (eg. Types 430 and 440)
sigma formation due to high (10-40%) ferrite content • Duplex SS
Critical • Alloy composition • Precipitation of a hard, brittle intermetallic compound ;
factors • Time of exposure at elevated temp precipitation rate increases with increase of Cr and Mo content
• Temperature range 538 to 954degC
• Damage occur in ferritic (Fe-Cr), martensitic (Fe-Cr), austenitic
(Fe-Cr-Ni) and duplex SS
Affected • SS cyclones, piping ductwork and valves in high temp FCC regenerator service
units / • 300 Series SS weld overlays and tube-tubesheet attachment welds can be embrittled during PWHT treatment of CrMo base metal
equipment • SS heater tubes

Appearance • Not readily apparent

or • Require metallographic exam
morphology • Impact test
of damage • Damage appears as cracking at welds or high restraint areas
• Cast austenitic SS have high ferrite/sigma content (up to 40%) and may have very poor high temp ductility
Prevention / • Use alloys that are resistant
Mitigation • Avoid exposing to embrittling range
• Avoid high stresses to sigmatized materials during shutdown
• For 300 Series SS, de-sigmatize by solution annealing at 1066degC for 4 hours, followed by water quench
• Sigma phase in welds can be minimized by controlling ferrite btw 5% to 9% for type 347, and less ferrite for type 304
• For SS weld overlay clad Cr-Mo components, limit the exposure time to PWHT
Inspection & • Physical test of samples removed from service
monitoring • Cracking in wrought and cast (welded) metals during turnarounds, startup or shutdown, when the material is below 260degC

Related • NA
mechanisms

Internal
 Mechanical & Metallurgical Failure Mechanism

Brittle Fracture
Description • Sudden rapid fracture under stress (residual or applied)
of damage • Material shows little or no evidence of ductility or plastic
deformation

Affected • CS • Older steels

materials • Low Alloy steels • 400 Series SS
Critical • Critical combination of 3 factors: • Presence of embrittling phases
factors • Facture toughness as measured in Charpy impact test • Steel cleanliness and grain size
• Size, shape and stress concentration effect • Thickness – more thick -> lower resistance
• Amount of residual and applied stressess • Occurs at temp below Charpy impact transition temp

Affected • Equipment manufactured to ASME 8 Div 1 prior to December 1987 addenda

units / • Equipment made to the same code after the date were subjected to the UCS 66 (impact exemption curves)
equipment • Main concern during startup, shutdown or HT/tightness test
• Can occur during autorefrigeration event in units processing light HC; alkylation units, olefin units, polymer plants (polyethylene and
polypropylene)
• Storage bullets/spheres
• Can occur at ambient temp hydrotesting due to high stresses and low toughness at test temp
Appearance • Cracks are straight
or • Non-branching
morphology • Largely devoid of plastic deformation (no shear lip or localized necking around the crack)
of damage • Microscopically, fracture surface will have large cleavage, with limited intergranular cracking and very little microvoid coalescence

Prevention / • For new equipment

Mitigation • Use materials designed for low temp operation including upset and autorefrigeration events. Refer to UCS 66 in ASME 8
• Engineering study per API RP 579, Section 3, Level 1 or 2
• Control operating conditions (pressure, temp) minimizing pressure at ambient temp during startup and shutdown
• Periodic inspection at high stress locations
• PWHT on vessel if not originally done during mfg, or if vessel been weld repaired / modified while in service
• Perform “warm” pre-stress HT followed by lower temp HT to extend Minimum Safe Operating Temp (MSOT) envelope
Inspection & • Inspect for pre-existing flaws / defects
monitoring

Related • Temper embrittlement • Titanium hydriding

mechanisms • Strain age embrittlement • Sigma embrittlement
• 885degF (475degC) embrittlement
Internal
Internal
Internal
 Mechanical & Metallurgical Failure Mechanism

Creep & Stress Rupture

Description • Creep:- • Deformation leads to damage that may eventually lead to a
of damage • At high temperature rupture
• Metal slowly and continuously deform under load below
yield stress
• Time dependent deformation
• Stressed component
Affected • All metal and alloys
materials

Critical • Rate of creep deformation: • Low creep ductility:

factors • Function of material, load & temperature • More severe for higher tensile strength materials/welds
• Rate of damage (strain rate): • More prevalent at lower temps in creep range, or low
• Sensitive to both load & temperature stresses in upper creep range
• In general, increase of 12degC or increase f 15% on stress can cut • More likely in coarse-grained material
the remaining life in half or more (depending on alloy) • Not evidenced by deterioration of ambient temp
• Life of metal components becomes NEARLY INFINITE at temps properties
below threshold limit (Table 4-2) even at high stresses near a • Promoted by certain carbide types in some CrMo steels
crack tip
Affected • High temp equipment operating above creep range – heater tubes in fired heaters, tube supports, hangers, other furnace internals
units / • Piping & equipment operating in or near the creep range – hot-wall catalytic reforming reactors, furnace tubes, hydrogen reforming
equipment furnace tubes, hot wall FCC reactors, FCC main fractionator, regenerator internals
• Low creep ductility failure can occur in weld HAZ at nozzles and other high stress areas on catalytic reformer reactors.
• Cracking can occur at long seam welds in high temp piping & reactors on catalytic reformers
• Welds joining dissimilar materials (ferritic to austenitic welds) may have creep damage at high temp due to differential thermal expansion
stresses
Appearance • Initial stage  scan using electron microscope metalography – creep voids can be found at grain boundaries in the later stages form
or fissures & then cracks
morphology • At temps above threshold limit, noticeable deformation may be observed – eg. Heater tubes may suffer long term creep damage and have
of damage SIGNIFICANT BULGING before FINAL FRACTURE
• In vessels & piping  creep cracking due to high metal temp & stress concentrations occur together – near major structural discontinuities
including pipe tee joints nozzles or welds at flaws
• Creep cracking, once initiated, can progress rapidly

Internal
 Mechanical & Metallurgical Failure Mechanism

Creep & Stress Rupture

Prevention / • When in service  minimize metal temp
Mitigation • Design & fabrication  avoid stress concentrators
• Minimize low creep ductility
• Careful selection of chemistry for low alloy materials
• Higher PWHT temps to minimize creep cracking
• Not reversible
• Higher PWHT in some cases may produce creep ductile material with longer life
• Equipment – Repair of creep damaged catalytic reformer reactor nozzles has been done by
• Griding out affected area
• Re-welding
• Careful blend grinding to minimize stress concentration
• Carefully select PWHT temps – may require higher PWHT than originally specified
• Fired heater tubes
• Select alloys with improved creep resistance
• Design & operation to minimize hot spots and localized overheating
• Visual inspection, thickness measurements, and/or strap readings – API RP 579
• Minimize process side fouling / deposits & fire side deposits / scaling
Inspection & • Combination of techniques – UT, RT, EC, dimensional measurements & replication
monitoring • Destructive sampling and metallographic exam – to confirm damage
• For pressure vessels
• Focus inspection on welds of CrMo alloys
• 1Cr-0.5Mo and 1.25Cr-0.5Mo are prone to low creep ductility
• Visual inspection, PT / WFMT on several year intervals
• Angle beam (shear wave) UT
• Initial fabrication flaws should be mapped and documented for future reference
• Fired heater tubes’ inspection
• VT exam for bulging, blistering, cracking, sagging, bowing
• Wall thickness measurements
• Check diametric growth (creep) with strap or go/no go gauge / metallography on in place replicas or tube sample
Related • Creep damage due to exposure to very high temps, described in
mechanisms Stress Rupture
• Reheat cracking

Internal
Internal
 Mechanical & Metallurgical Failure Mechanism

Thermal Fatigue
Description • Result of cyclic stresses caused by temp variations • Under repeated thermal cycling
of damage • Cracking may occur anywhere where relative movement or
DIFFERENTIAL EXPANSION is contrained

Affected • All materials of construction

materials

Critical • Magnitude of temp swing • Rapid changes in surface temp (thermal gradient through
factors • Frequency of temp swing (no of cycles) thickness or along length – eg
• Startup & shutdown increase chances of thermal fatigue • Cold water on hot tube (thermal shock)
• No set limit on temp swings • Rigid attachments & smaller temp differential
• Practical rule; cracking may happen if temp swing exceeds 93degC • Inflexibility to accommodate differential expansion
• Initiation areas
• Notches (eg. weld toe)
• Sharp corners (eg. Intersection of nozzle & vessel shell)
• Other stress concentrations
Affected • Mix points of hot & cold streams
units / • Locations where condensate in contact with steam systems
equipment • De-superheating / attemporating equipment
• Coke drum shells & coke drum skirts
• Steam generating equipment – rigid attachments between tubes in superheater & reheater
• Tubes in superheater or reheater that penetrate through cooler waterwall tubes may crack at header connection
• Steam actuated soot blowers – if the first steam exiting the soot blower nozzle contains condensate
Appearance • Usually initiate on surface • In steam generating equipment
or • Wide • Cracks follow tow of fillet weld
morphology • often filled with oxides • Cracks start at end of attachment lug; circumferental
of damage • Single or multiple cracks cracks will develop if there is bending moment
• Crack propagates transverse to the stress • Water in soot blowers may lead to crazing patters – predominant
• Dagger-shaped cracks (circumferential) & minor cracks (axial)
• Transgranular
• Oxide filled
• Cracks may be axial or circumferential, or both, at the
same location

Internal
 Mechanical & Metallurgical Failure Mechanism

Thermal Fatigue
Prevention / • Design & operation
Mitigation • Use designs that reduce stress concentrators, blend grinding or weld profiles, smooth transitions
• Control rates of heating and cooling during startup and shutdown
• Consider differential thermal expansion between dissimilar materials
• Design should incorporate sufficient flexibility to accommodate differential expansion
• Steam generating equipments
• Slip spacers should slip
• Avoid rigid attachments
• Soot blowers
• Provide drain lines to prevent condensate
• Install liner or sleeve to prevent direct contact btw colder liquid & hotter pressure boundary wall
Inspection & • Surface cracking
monitoring • Visual exam
• MT
• PT
• Internal cracking or reinforcing pad prevent nozzle exam
• External SWUT (surface wave ultrasonic testing)
Related • Corrosion fatigue
mechanisms • Dissimilar weld metal cracking

Internal
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 Mechanical & Metallurgical Failure Mechanism

Short Term Overheating – Stress Rupture

Description • Permanent deformation • Results in bulging and eventually failure by stress rupture
of damage • Occur at relatively low stress levels
• Due to localized overheating

Affected • All fired heater tube materials

materials • Common materials of construction
Critical • Temp, time and stress • Local overheating above the design temp
factors • Flame impingement or local overheating • Loss in thickness due to corrosion  reduce time to failure by
• Internal pressure or loading decrease  time to failure increase increasing stress
• Temp increase  bulging & distortion significant at low stresses

Affected • All boiler and fired heater tubes

units / • Furnaces with coking tendencies – crude, vacuum, heavy oil hydroprocessing and coker units
equipment • Hydroprocessing reactors’ reactor beds
• Refractory lined equipment in the FCC, sulfur plant and other units

Appearance • Localized deformation or bulging, 3 – 10% or more, depending on alloy, temp and stress level
or • Ruptures are “fishmouth” failures and usually thinning at he fracture surface
morphology
of damage

Prevention / • Minimize localized temp • Hydroprocessing equipment

Mitigation • Fired heater • Install & maintain bed thermocouples in reactors
• Proper burner management • Minimize hot spots
• Fouling / deposit control • Maintain refractory in serviceable condition in refractory lined
• Use burners with diffuse flame pattern equipment
Inspection & • Fired heaters  monitor temp • Refractory lined equipment  monitor temp
monitoring • Visual observation • Heat indicating painting
• IR monitoring f tubes and tubeskin thermocouples • Periodic IR scans
• Maintain / monitor reactor bed thermocouples & reactor skid • Inspection during shutdowns
thermocouples
Related • Creep / stress rupture
mechanisms

Internal
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 Mechanical & Metallurgical Failure Mechanism

Steam Blanketing
Description • ;Operation of steam generating equipment  a balance btw heat • When the heat flow is disturbed, individual bubbles join to form a
of damage flow from fuel combustion & steam generation within waterwall steam blanket (Departure from Nucleate Boiling (DNB))
or generating tube • Tube rupture can occur rapidly due to overheating, within a few
• Flow of heat energy through tube wall results in formation of minutes
discrete steam bubbles (nucleate boiling) on the iD surface
• The moving fluid sweeps the bubbles away
Affected • CS
materials • Low alloy steels
Critical • Heat flux – due to flame impingement from misdirected or • Failure due to hoop stress in the tube from internal steam
factors damaged burners pressure at elevated temp
• Fluid flow – restriction due to pinhole leaks lower in the steam
circuit / dented tubes from slag falls  reduce fluid flow and lead
to DNB
Affected • Fired boilers • Superheaters
units / • Waste heat exchangers in sulfur plants • Reheaters
equipment • Hydrogen reformers
• FCC units

Appearance • Open burst, with fracture edges drawn to near knife-edge

or • Severe elongation of grain structure
morphology
of damage

Prevention / • Proper burner mgmt to minimize flame impingement

Mitigation • Proper BFW (boiler feedwater) treatment
• Visual inspection on tube for bulging

Inspection & • Proper burner management

monitoring

Related • Steam blanketing can cause caustic corrosion (caustic gouging)

mechanisms • Very similar characteristics in short term overheating

Internal
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 Mechanical & Metallurgical Failure Mechanism

Dissimilar Metal Weld (DMW) Cracking

Description • Occur in ferritic (CS or low alloy steel) side of a weld btw austenitic (300 Series SS) and ferritic material operating at high temp
of damage
Affected • Ferritic materials welded to austenitic SS
materials • Any material combinations that have widely differing thermal expansion coefficients
Critical • Type of filler metal • Heating & cooling rate
factors • Coefficients of thermal expansion differ by 30% or more • Time at temp
• Use of austenitic SS filler metal  higher stress on • Weld geometry
weldment • Poor geometry
• Metal temp • Excessive undercut
• Diffusion of carbon out of HAZ of ferritic material into • Thermal cycling
weld metal • DMW on 300 Series SS-ferritic steel  narrow region of high
• Temp of carbon diffusion  above 427 to 510 degC hardness at the weld toe  susceptible to sulfide stress cracking
• Ferritic/austenitic joints can have significant thermal & hydrogen stress cracking
expansion / thermal fatigue stresses at temp above
260degC
Affected • Fired heater applications where heater tube material are 5Cr or 9Cr to 300 Series SS
units / • Transition in hydroprocessing reactor outlet piping from overlaid low alloy CrMo nozzles or piping to solid 300 Series SS piping
equipment • All superheaters and reheaters with welds btw ferritic materials (1.25Cr-0.5Mo and 2.25Cr-1Mo) & austenitic materials (300 Series SS,
304H, 321H, & 347H)
• Weld joining tubes, support lugs, attachments of cast or wrought 300 Series SS to 400 Series SS
Appearance • Cracks at weld toe in HAZ of ferritic material
or
morphology
of damage
Prevention / • Use nickel base filler metals  coefficient thermal expansion • For steam generating equipment  weld at high temp end to be
Mitigation closer to CS and low alloy steels made in the penthouse or header enclosure
• For 300 Series SS welding electrodes  to locate DMW in a low • Install pup piece with intermediate thermal expansion coefficient
temp region btw 2 materials
Inspection & • For external cracks in fired heater tubes  Visual, MT, PT
monitoring

Related • Thermal fatigue

mechanisms • Corrosion fatigue

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 Mechanical & Metallurgical Failure Mechanism

Thermal Shock
Description • Occur when high & non-uniform thermal stresses develop in short time due to differential expansion / contraction.
of damage • If the expansion / contraction is restrained  stresses above yield strength can happen
• Usually occurs when colder liquid contacts warmer metal surface
Affected • All metals & alloys
materials
Critical • Magnitude of temp differential + coefficient of thermal expansion • Fracture  casued by constraint on component that prevents it
factors  magnitude of stress from expanding or contracting with temp change
• Cyclic stresses (by temp cycling)  start fatigue cracks • Cracking in cast components (valves)  may start at internal
• SS hv higher coefficients of thermal expansion than CS & alloy casting flaws
steels / nickel base alloys  higher stresses • Thick section  high thermal gradients

Affected • FCC, cokers, catalytic reforming, high severity hydroprocessing units

units / • High temp piping & equipment
equipment • Materials that has lost ductility (CrMo equipment due to temper embrittlement)
• Accelerated cooling procedures to minimize shutdown time

Appearance • Surface initiating cracks  “craze” cracks

or
morphology
of damage
Prevention / • Prevent interruptions in the flow of high temp lines • Minimize rain or firewater deluge situations
Mitigation • Design to minimize severe restraint • Review hot/cold injection points
• Install thermal sleeves to prevent liquid impingement on the
pressure boundary components
Inspection & • Highly localized and difficult to locate
monitoring • PT & MT

Related • Thermal fatigue

mechanisms

Internal
 Mechanical & Metallurgical Failure Mechanism

Erosion / Erosion-Corrosion
Description • Erosion  accelerated mechanical removal of surface material, due to relative movement / impact from solids, liquids, vapor
of damage • Erosion-Corrosion  corrosion causes erosion by removing protective films / scales, or by exposing metal surface
Affected • All metals, alloys, and refractories
materials
Critical • Metal loss rates depends on • Corrosivity of environment
factors • Velocity, shape, density & concentration of impacting • Reduce stability of protective surface films
medium (particles, liquids, droplets, slurries, 2-phase • Metal removed from surface as dissolved ions
flow) • Increase in corrosivity of the environment due to temp,
• Size & hardness of impacting particles pH
• Hardness & corrosion resistance of material
• Angle of impact
• Softer alloys subject to severe metal loss (eg. Copper & aluminium
alloys)
Affected • All equipment exposed to moving fluids and/or catalyst  piping • In refineries
units / systems • Catalyst movement in FCC reactor / regenarator systems
equipment • Gas borne catalyst particles or slurry can cause erosion • Slurry piping
• Coke handling equipment in delayed & fluidized bed
cokers
• Wear on pumps, compressors, etc
Appearance • Localized loss in thickness (pits, grooves, gullies, waves, rounded holes & valleys)  exhibits directional pattern
or • Failures can happen in relatively short time
morphology
of damage
Prevention / • Design change • Improve resistance to erosion
Mitigation • Shape, geometry, materials selection • Increase substrate hardness using harder alloys
• Eg. Increase pipe dia to decrease velocity • Hardfacing or surface-hardening treatments
• Streamlining bends to reduce impingement • Improve resistance to erosion-corrosion
• Increase wall thickness • Use more corrosion-resistant alloys
• Use replaceable impingement baffles • Alter process environment
• Use of impingement plates & tube ferrules in heat exchangers • Deaeration
• Use higher molybdenum containing alloys  improve resistance • Condensate injection
to naphthenic acid corrosion • Addition of inhibitors

Internal
 Mechanical & Metallurgical Failure Mechanism

Erosion / Erosion-Corrosion
Inspection & • Visual exam
monitoring • UT or RT to detect extent of metal loss
• Specialized corrosion coupons
• On-line corrosion monitoring electrical resistance probes
• IR scans to detect refractory loss on stream
Related • Specialized terminology for various forms of erosion & erosion-
mechanisms corrosion
• Cavitation
• Liquid impingement erosion
• Fretting

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 Mechanical & Metallurgical Failure Mechanism

Cavitation
Description • A form of erosion
of damage • Cause  formation & instantaneous collapse of innumerable tiny vapor bubbles
• Exert severe localized impact forces  metal loss
• Bubbles may contain  vapor phase of liquid, air or other gas
Affected • Copper and brass • 300 Series SS
materials • Cast iron • 400 Series SS
• CS • Nickel base alloys
• Low alloy steels
Critical • Sufficient NPSHr  min head required to prevent cavitation • Bubble formation  due to temp near liquid’s boiling point
factors • Inadequate NPSH can result in cavitation • Presence of solid or abrasive particles  accelerate the damage
Affected • Damage observed in • Example of affected equipment
units / • Pump casings • HEX tubes
equipment • Pump impellers (low pressure side) • Venturis
• Piping downstream of orifice or control valves • Seals & bearings
• Restricted flow passages • Impellers
• Areas where turbulent flow is subjected to rapid pressure • Only occur in localized low-pressure zones
changes within a localized region
Appearance • Sharp-edged pitting
or • Gouged appearance
morphology
of damage
Prevention / • Not significantly improved with material change • Attack accelerated by  MECHANICAL DISRUPTION of protective
Mitigation • Avoid absolute pressure to fall below vapor pressure of the liquid films at liquid-solid interface (protective corrosion scale or passive
OR by changing the material properties films)
• Streamline flow path to reduce turbulence • Changing to more corrosion resistant and/or higher
• Decrease fluid velocities hardness material may NOT IMPROVE cavitation
• Remove entrained air resistance
• Increase pump’s suction pressure • The hard materials require the toughness to withstand
• Alter fluid properties  adding additives high local pressures and impact (shear loads) of the
• Use hard surfacing or hardfacing collapsing bubbles
• Use harder and/or more corrosion resistant alloys

Internal
 Mechanical & Metallurgical Failure Mechanism

Cavitation
Inspection & • Sound like pebbles being thrashed around inside
monitoring • Limited monitoring of fluid properties
• Acoustic monitoring of turbulent areas
• Visual exam, UT & RT  monitor loss in thickness
Related • Liquid impingement or erosion
mechanisms

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 Mechanical & Metallurgical Failure Mechanism

Mechanical Fatigue
Description • A mechanical form of degradation
of damage • Occur when component exposed to cyclical stresses for extended period
• Sudden, unexpected failure
Affected • All engineering alloys
materials • Stress levels and no of cycles to cause failure vary by material
Critical • Geometry & Design • Stress level
factors • Surface features that can initiate fatigue cracks • No of cycles
• Mechanical notches (sharp corners or groves) • CS & Titanium  fatigue crack will not occur below
• Key holes on drive shafts of rotating equipment endurance limit, regardless of no of cycles
• Weld joint, flaws and/or mismatches • For titanium, CS & low alloy steel  no of cycles to
• Quench nozzle areas fracture decreases with stress amplitude
• Tool markings • Material properties (strength, hardness, microstructure)
• Grinding marks • 300 Series SS, 400 Series SS, aluminium & most other
• Lips on drilled holes non-ferrous alloys
• Thread root notches • Do not have endurance limit
• Corrosion • Fatigue fracture will happen under cyclical
• Metallurgical issues & microstructure loading, regardless of stress amplitude
• For alloys with endurance limits  ratio of • Max cyclical stress amplitude to cause fracture in
endurance limit over UTS (ultimate tensile component’s lifetime  btw 10exp6 to 10exp7
strength) is btw 0.4-0.5
• Older, “dirty” steels or weldments  may have
inclusions which will accelerate fatigue crack
• Heat treatment  fine-grained perform better
than coarse-grained
Affected • Thermal cycling • Mechanical loading
units / • Cycles daily in operation, eg. Coke drums • Rotating shafts on centrifugal pumps & compressors
equipment • Auxiliary or continuous standby, eg. Auxiliary boiler • Small dia piping with vibration issues
• Quench nozzle connections , eg. Water washing system • High pressure drop control valves or steam reducing
stations may cause serious vibration
Appearance • “Clam shell” type fingerprint with concentric rings (“beach marks”) emanating from crack initiation
or • Single “clam shell”  cracks initiated from a surface stress concentration or defect
morphology • Multiple “clam shell”  cracks due to cyclical overstress without significant stress concentration
of damage

Internal
 Mechanical & Metallurgical Failure Mechanism

Mechanical Fatigue
Prevention / • Good design that minimizes stress concentration of components • Minimize grinding marks, nicks, & gouges
Mitigation in cyclic services • Welds  Good fit-up & smooth transitions; minimize weld
• Metal selection  sufficient design fatigue life for intended cyclic defects
service • Remove burrs or lips caused by machining
• Ample radius along edges & corners • Use low stress stamps & marking tools

Inspection & • To detect fatigue cracks at known areas of stress concentration 

monitoring PT, MT, SWUT (shear wave ultrasonic testing)
• To detect oscillation or other cyclical movement  VT for small
diameter piping
Related • Vibration induced fatigue
mechanisms

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 Mechanical & Metallurgical Failure Mechanism

Vibration-Induced Fatigue
Description • A form of mechanical fatigue
of damage • Cracks happen as a result of dynamic loading (vibration, water hammer, unstable fluid flow)
Affected • All engineering materials
materials
Critical • Amplitude of vibration • Materials’ fatigue resistance
factors • Frequency of vibration • Lack of or excessive support or stiffening
• High likelihood of cracking  synchronous input load or
nearly synchronizes with component’s natural frequency

Affected • Socket welds & small bore piping at or near pumps & compressors • Small branch connections with unsupported valves or controllers
units / that are not sufficiently gusseted • Safety relief valves subjected to chatter, premature pop-off,
equipment • Small bore bypass lines & flow loops around rotating & fretting, and failure
reciprocating equipment • High pressure drop control valves & steam reducing stations
• HEX tubes susceptible to vortex shedding
Appearance • Damage in the form of crack at point of high stress or discontinuity; eg thread or weld joint
or • For refractories  visible damage from the refractory failure (high skin temperatures) and/or anchoring system
morphology
of damage
Prevention / • Design & use of supports & vibration dampening eqpmt • Vibration effects
Mitigation • Material upgrades are not usually a solution • To anchor vibrating section
• At small bore connections • Require special study before providing anchor or
• Install gusset or stiffeners dampeners
• Inspect field installations • Eliminate the vibrating source
• At outlet of control valves & safety valves
• Minimize vortex shedding
• Proper side branch sizing
• Flow stabilization techniques
Inspection & • Look for visible signs of vibration, pipe movement or water • Measure pipe vibrations
monitoring hammer • Use surface inspection method PT, MT
• Check audible sounds of vibration • Check pipe supports & spring hangers
• Conduct visual inspection during startups, shutdowns, upsets for • Damage to insulation jacketing may indicate excessive vibration
intermittent vibrating conditions
Related • Mechanical fatigue
mechanisms • Refractory degradation

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 Mechanical & Metallurgical Failure Mechanism

Refractory Degradation
Description • Both thermal insulating & erosion resistant refractories are exposed to mechanical damage (cracking, spalling, erosion) & corrosion (due
of damage to oxidation, sulfidation, & other high temp mechanisms)
Affected • Refractory materials (insulating ceramic fibers, castables, refractory brick, plastic refractories)
materials
Critical • Refractory selection • Refractory design
factors • Type & density must be selected to resist abrasion & • Lined eqpmt should consider erosion, thermal shock,
erosion thermal expansion
• Refractory installation as per mfr spec & ASTM • Anchor materials to be compatible with thermal
• Dry out schedules coefficients of expansion of base metal
• Cure times • Anchors must be resistant to oxidation in high temp
• Application procedures services & condensing sulfurous acids in heaters & flue
gas environments
• Needles & other fillers must be compatible with process
environment composition & temp
Affected • Refractories are extensively used
units / • in FCC reactor regenerator vessels, piping, cyclones, slide valves & internals
equipment • in fluid cokers
• in cold shell catalytic reforming reactors
• in waste heat reboilers & thermal reactors in sulfur plants
• Boiler fire boxes & stacks which use refractory
Appearance • Excessive cracking, spalling or lift-off from the substrate, softening or general degradation from exposure to moisture
or • Coke deposits may develop behind refractory & promote cracking & deterioration
morphology • In erosive services, refractory may be washed away or thinned, exposing the anchoring system
of damage
Prevention / • Proper selection of refractory, anchors, and fillers
Mitigation • Proper design
• Proper installation

Inspection & • Visual inspection during shutdowns

monitoring • IR  survey cold-wall eqpmt onstream to monitor hot spots

Related • Oxidation
mechanisms • Sulfidaton
• Flue gas dew point corrosion

Internal
 Mechanical & Metallurgical Failure Mechanism

Reheat Cracking
Description • Cracking of a metal due to stress relaxation during PWHT or in service at elevated temp
of damage • Most observed in heavy wall sections
Affected • Low alloy steels
materials • 300 Series SS
• Nickel base alloys (Alloy 800H)
Critical • Type of material (chemical composition, impurity elements)
factors • Grain size
• Residual stresses from fabrication (cold working, welding)
• Section thickness (which controls restraint & stress state)
• Notches & stress concentrators
• Weld metal & base metal strength
• Welding & heat treating conditions
Affected • Heavy wall vessels in areas of high restraint including nozzle welds & heavy wall piping
units / • HSLA (high strength low alloy) steels
equipment

Appearance • Intergranular
or • Can be surface breaking or embedded
morphology • Observed in coarse-grained sections of weld’s HAZ
of damage
Prevention / • Design joint config in heavy wall sectionsto minimize restraint during welding & PWHT. Adequate pre-heat must be applied
Mitigation • Avoid large grain size
• Metallurgical notches from welding operation  causing HAZ cracking
• In design & fab, avoid sharp changes in cross section (eg. Short radius fillets or undercuts)
• Long-seam welds are susceptible to mismatch caused by fitup problems
Inspection & • Surface cracks in CS & low alloy steels  UT & MT
monitoring • Cracks in 300 Series SS & nickel base alloys  UT & PT
• Embedded cracks  UT
Related • Has been referred to as “stress relief cracking” & “stress relaxation cracking”
mechanisms

Internal
 Uniform or Localized Loss of Thickness

Internal
 Uniform or Localized Loss of Thickness

Galvanic Corrosion
Description • Corrosion at the junction of dissimilar metals
of damage • When these metals are joined in a suitable electrolyte (moist / aqueous / soils with moisture)
Affected • All metals with exception of most noble metals
materials
Critical • 3 conditions must be met • Affect of relative exposed surface areas btw anodic & cathodic
factors • Electrolyte • Small anode to cathode ratio  high corr rate of anode
• 2 different materials or alloys (anode & cathode) in • Large anode to cathode ratio  less corr rate of anode
contact with electrolyte • Coat the more noble material; if anode were coated, large
• Electrical connection btw anode & cathode cathode to anode area can accelerate corr of anode at
• Table 4-4 any coating defects
• The same alloy may act as both anode & cathode due to
• Surface films
• Scale
• Local environment
Affected • Any unit where there is a conductive fluid and alloys are coupled
units /
equipment
Appearance • The anode can suffer • Anode may corrode significantly higher immediately adjacent to
or • Generalized loss in thickness the cathode
morphology • Crevice
of damage • Groove
• Pitting
Prevention / • Good design
Mitigation • Differing alloys should not be in contact, unless anode/cathode surface area ratio is favorable
• Coat the more noble material
• Use specially designed electric insulating bolt sleeves & gaskets in piping

Inspection & • Visual

monitoring • UT
Related • Soil corrosion
mechanisms

Internal
 Uniform or Localized Loss of Thickness

Galvanic Corrosion

Internal
 Uniform or Localized Loss of Thickness

Corrosion Under Insulation (CUI)

Description • Corrosion on surface due to water trapped under insulation or fireproofing
of damage
Affected • CS, low alloy steels, 300 Series SS, duplex SS
materials
Critical • Design of insulation system : poor design that allow water trap • Operation temp
factors • Insulation type • Cyclic or intermittent ↑ corrosion
• Materials that can hold moisture (wick) • Environment (humidity, rainfall, chlorides from marine, high SO2
• Metal temperature environment)
• Metal temp ↑, Corr rate ↑ • Operation below water dew point  condense water on
• More severe corr : 100degC < Metal temp < 121degC  metal surface
water less likely to vaporize • Contaminants from insulation (eg chlorides)
• In marine environment, CUI upper temp range extends • High annual rainfall or warmer, marine
significantly above 121degC  moisture presence • Airborne contaminants, eg chlorides (marine, cooling
tower drift) or SO2 (stack emissions)
Affected • CS & low alloy steels  pitting & thickness loss • Damaged/leaking steam tracing
units / • 300 Series SS, 400 Series SS, Duplex SS  pitting & localized corr • Localized damage at paint and/or coating systems
equipment • 300 Series SS  SCC if chlorides are present • Gravity drainage  natural moisture/water collector
• Insulation damage or protrusions • 1st few feet of horizontal pipe run adjacent to bottom or vertical
• Insulation support rings welded to vessel wall; around ladder, pipe run
platform clips, lifting lugs, nozzles, stiffener rings
Appearance • CS & low alloy steel • 300 Series SS, in older calcium silicate insulation (known to
or • Loose, flaky scale covering corroded component contain chlorides)
morphology • Highly localized (Fig 4-38, 4-39) • Localized pitting
of damage • Carbuncle type pitting (under failed paint/coating) • Chloride stress corrosion cracking

Prevention / • Best achieved using appropriate paints/coatings & maintain • Use low chloride insulation on 300 Series SS  minimize pitting
Mitigation insulation/sealing/vapor barriers and chloride SCC
• Careful insulating material selection : Closed-cell foam glass • Remove insulation where heat conservation is not as important
materials hold less water against vessel / pipe wall than mineral
wool  potentially be less corrosive

Internal
 Uniform or Localized Loss of Thickness

Corrosion Under Insulation (CUI)

Inspection & • Inspection plan (structured & systematic) • Partial / full stripping of insulation for visual
monitoring • Prediction/analysis • UT
• Invasive approach • Real-time X-ray (for small bore piping)
• Neutron backscatter techniques for identifying wet insulation
• Deep penetrating eddy-current inspection (can be automated
with robot crawler)
• IR thermography looking for wet insulation / damaged insulation
under jacket
• Guided wave UT
Related • Atmospheric corrosion, oxidation, and chloride SCC
mechanisms

Internal
 Uniform or Localized Loss of Thickness

Cooling Water Corrosion

Description • General or localized corrosion • Caused by mineral deposits (hardness), silt, dissolved salts, gases, mill
of damage • For CS & other metals scale, marine suspended organic materials or microbiological growth
Affected • CS • Aluminium
materials • SS – all grades • Titanium
• Copper • Nickel-based alloys
Critical • Fluid temperature • Copper/zinc alloys  dezincification, & SCC
factors • ↑ cooling water outlet temp and/or process side • ERW CS  severe weld, HAC corr
inlet temp  ↑ fouling tendency • Oxygen content
• Type of water (fresh, brackish, salt water) • ↑ oxygen  ↑ CS corr rates
• Fresh water  scaling potential if process side • Fluid velocities
temp > 60C • Should be high enough to minimize fouling & drop out deposits
• Brackish & salt water  serious scaling if outlet • Depends on tube material & water quality
temp 46C • Vel < 1m/s  fouling, sedimentation, increased corrosion in
• Type of cooling system (once-through, open circulating, fresh & brackish water systems
closed circulating) • Accelerated corr at dead spots or stagnant areas if cooling water
• 300 Series SS  pitting, crevice corr, & SCC is used at shell side
Affected • Water-cooled HEX
units / • Cooling towers
equipment
Appearance • If there is dissolved oxygen  general or uniform corr of CS • MIC
or • Localized corr  Underdeposit corr, crevice corr, or • SCC
morphology microbiological corr • Fouling
of damage • If there is deposits or crevices  underdeposit or crevice corr • Flow induced corr, erosion, abrasion  wavy or smooth corr at
• Pitting corrosion (Fig 4-40) nozzle inlets/outlets & tube inlets
• Corr at ERW welds areas  grooving along weld fusion
Prevention / • Proper design, operation & chemical treatment • Improve material selection for HEX parts in high chloride content
Mitigation • Design for process side inlet temp < 57C water, low velocity, high process temp, poor water chemistry
• Maintain min & max water velocities • Design cooling water in tube side
Inspection & • Monitor pH, oxygen content, cycles or concentration, biocide • Ultrasonic flowmeters to check water velocity
monitoring residual, biological activity, cooling water outlet temp, HC • EC or IRIS inspection of tubes
contamination & process leaks • Splitting representatives tubes
• Periodic calc of U-factors (HEX performance measurement)
Related • Microbiologically induced corrosion, Chloride SCC, Galvanic corrosion
mechanisms

Internal
 Uniform or Localized Loss of Thickness

Cooling Water Corrosion

Internal
 Uniform or Localized Loss of Thickness

CO2 Corrosion
Description • Caused by CO2 dissolves in water, forming carbonic acid (H2CO3)
of damage • Acid lower the pH  promote general corr and/or pitting corr
Affected • CS
materials • Low alloy steels
Critical • Partial pressure of CO2 : ↑ CO2 partial pressure  pH ↓ & corr rate ↑
factors • pH
• Temperature : ↑ temp  corr rate ↑ until CO2 vaporizes
Affected • Boiler feedwater
units / • Condensate system
equipment • Effluent gas streams of the shift converters in hydrogen plants
• Overhead systems of regenerators in CO2 removal plants
Appearance • Localized thinning and/or pitting corr of CS (Fig 4-41, 4-42, 4-43)
or • Deep pitting and grooving in areas of turbulence in CS (Fig 4-44)
morphology • Corrosion occurs in areas of turbulence & impingement, & sometimes at root of piping welds
of damage
Prevention / • Increasing chromium level in steels have no major improvement in corr resistance until a min of 12%
Mitigation • Use corrosion inhibitors in steam condensate system. May require vapor phase inhibitors
• Increase condensate pH > 6 in steam condensate system
• Use 300 Series SS, 400 Series SS, and duplex SS
Inspection & • VT, UT, & RT on general and local loss in thickness in water wetting areas
monitoring • Angle probe UT or RT to detect preferential corrosion of weld seams
• Monitor water analyses (pH, Fe, etc)
Related • Boiler water condensate corrosion
mechanisms • Carbonate cracking

Internal
 Uniform or Localized Loss of Thickness

CO2 Corrosion

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 General – Environment-Assisted Cracking

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 General - Environment-Assisted Cracking

Chloride Stress Corrosion Cracking (Cl-SCC)

Description • Surface initiated cracks • Dissolved oxygen will increase propensity for cracking
of damage • Under combined action of
• Tensile stress
• Temperature
• Aqueous chloride environment
Affected • All 300 Series SS are HIGHYLY SUSCEPTIBLE • Duplex SS are MORE RESISTANT
materials • Nickel base alloys are HIGHLY RESISTANT
Critical • Chloride content : ↑chloride level  ↑cracking likelihood • Alloy composition
factors • pH : SCC at pH > 2; SCC tendency drops toward alkaline pH • Nickel
• Temperature : ↑temp  ↑cracking susceptibility; Usually at • Greatest susceptibility  Ni = 8 to 12%
metal temp > 60degC • Highly resistant  Ni > 35%
• Stress : Applied stress or Residual stress • Nearly immune  Ni > 45%
• Presence of oxygen : Dissolved oxygen in water accelerates SCC • Low-nickel SS (eg Duplex SS)  improved resistance vs
300 SS but not immune
• NOT SUSCEPTIBLE TO Cl-SCC : CS, low-alloy steels, 400
Series SS
Affected • All 300 Series SS piping & pressure vessel components in any • Bellows & instrument tubing (hydrogen recycle streams
units / process units contaminated with chlorides)
equipment • Water-cooled condensers • External Cl-SCC on insulated surfaces
• Drains in hydroprocessing units • Boiler drain lines

Appearance • Surface breaking cracks – internally and externally under • Branched transgranular cracks (Fig 4-81, 4-82)
or insulation (Fig 4-77) • Brittle appearance
morphology • Craze-cracked appearance of surface (Fig 4-78, 4-79, 4-80)
of damage
Prevention / • Use resistant materials • Proper coatings
Mitigation • Use low chloride content water and do thorough&quick dryout • Avoid stagnant regions
for HT • High temp stress relief of 300 Series SS

Inspection & • Visual • UT

monitoring • PT or phase analysis EC • RT is not sensitive except in advance stage
• Eddy current inspection

Related • Caustic SCC and Polythionic acid SCC

mechanisms

Internal
 General - Environment-Assisted Cracking

Chloride Stress Corrosion Cracking (Cl-SCC)

Internal
 General - Environment-Assisted Cracking

Chloride Stress Corrosion Cracking (Cl-SCC)

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 Refining Industry -
Environment-Assisted Cracking

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 Refining Industry - Environment-Assisted Cracking

Polythionic Acid Stress Corrosion Cracking (PASCC)

Description • A form of stress corrosion cracking • Usually adjacent to welds or high stress areas
of damage • Occur during shutdowns, startups or during operation when air & • Cracking propagate rapidly through wall thickness of piping &
moisture are present components in minutes or hours
• Cracking due to sulfur acids forming from sulfide scale, air &
moisture acting on sensitized austenitic SS
Affected • 300 Series SS • Alloy 800/800H
materials • Alloy 600/600H
Critical • Combination of environment, material & stress: • Alloys is sensitized 
factors • Environment • exposure to elevated temp during manufacture, welding
• Metal + sulfur  surface sulfide scale or high temp service
• Scale + air (oxygen) + moisture  sulfur acids • Composition/time/temp dependent formation of
(polythionic acid) chromium carbide in metal’s grain boundaries
• Material – in a “sensitized” condition • 400 to 815degC
• Stress – Residual or applied • Sensitization susceptibility depend on C content & alloy’s
• Residual stresses usually sufficient to promote cracking thermal history
• Regular & controlled carbon grades of SS (304/304H &
316/316H)  sensitizing in HAZ
• Low Carbon “L” grades (<0.03%C)
• Less susceptible
• Can be welded WITHOUT SENSITIZING
• Will NOT SENSITIZE as long operating temp <
399degC

Affected • All units where sensitized alloys used in sulfur-containing environments  HEX tubes, furnace tubes, piping
units / • Fired heaters burning oil, gas, coke & most other sources of fuel  depend on sulfur levels
equipment • FCC units (air rings, plenums, slide valves, cyclone components, expansion joint bellows & piping)
• Hydroprocessing units  heater tubes, hot feed/effluent exchanger tubes, bellows
• Crude & coker units (piping)
• Boilers & high temp eqpmt exposed to sulfur-containing combustion products
Appearance • Typically occurs next to welds, but can also occur in base metal
or • Quite localized
morphology • May not be evident until leak appears during startups or operation
of damage • Crack propagates intergranularly
• Corrosion or loss in thickness is negligible

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 Refining Industry - Environment-Assisted Cracking

Polythionic Acid Stress Corrosion Cracking (PASCC)

Prevention / • If equipment will be opened or exposed to air
Mitigation • Refer NACE RP0170
• Flush with alkaline or soda ash solution  neutralize sulfur acids
• Purge with dry nitrogen or nitrogen/ammonia during shutdown  prevent air exposure
• For furnaces
• Heat firebox above dewpoint  prevent acids from forming on heater tubes
• Material selection – use Low C grades (304L/316L/317L)  L grades with only sensitize if exposed to more than several hours above
538degC or long term above 400degC
• Use modified alloys containing some Ti & Nb
• Chemically stabilized grades (austenitic SS types 321 & 347)
• Nickel base alloys 825 & 625
• ASTM specs
• Allow mill products to be shipped in STABILIZED CONDITIONS vs solution annealed
• This will minimize potential sensitization problems (especially type 321)
• Thermal stabilization heat treatment at 899degC for chemically stabilized austenitic SS welds  reduce sensitization & PTA (polythionic
Acid) susceptibility
• Lab corrosion testing (ASTM A262 Practice C) –apply sensitizing heat treatment to L and/or chemically stabilized grade before test

Inspection & • PT, but cracks are filled with tight deposit – to improve PT sensitivity, use flapper disc sanding
monitoring • Crack might not occur until well into turnaround
• No monitoring for PASCC during operation
Related • Polythionic Acid Streaa Corrosion Cracking (PTA SCC)
mechanisms • Intergranular Corrosion (IGC)
• Intergranular Attack (IGA)

Internal
Internal
Internal
 Refining Industry - Environment-Assisted Cracking

Amine Stress Corrosion Cracking

Description • Cracking under combined action of tensile stress & corrosion in aqueous alkanolamine systems
of damage • A form of alkaline stress corrosion cracking
• Found at or adjacent to non-PWHT’d CS weldments or in highly cold worked parts
Affected • CS & low alloy steels
materials
Critical • Level of tensile stress, amine concentration & temp
factors • Main reason is residua l stresses that are not removed by stress-
relieving heat treatment
• Occur in lean MEA & DEA, but also found in MDEA & DIPA (ADIP)
• Cracking mostly found in lean amine services
• Cracking can occur in non-PWHT’d piping & eqpmt  due to
steamout & to short-term amine carryover

Affected
units /
equipment

Appearance
or
morphology
of damage
Prevention /
Mitigation

Inspection &
monitoring

Related
mechanisms

Internal
 Refining Industry - Environment-Assisted Cracking

Wet H2S Damage (Blistering/HIC/SOHIC/SSC)

Description • Hydrogen blistering
of damage • Surface bulges on ID, OD, within wall
• How blisters are created?
• During sulfide corrosion process on the steel’s surface, hydrogen atoms are formed
• Hydrogen atoms diffuse into the steel, & collected at steel’s discontinuity (inclusion or lamination)
• The hydrogen atoms combine forming hydrogen molecules that are too large to diffuse out, & the pressure builds to the
point of local deformation, forming a blister
• Blistering results from hydrogen generated by corrosion, NOT hydrogen gas from the process stream

• Hydrogen Induced Cracking (HIC)

• Hydrogen blisters can form at many different depths from the surface of steel, middle of plate, or near a weld
• Adjacent blisters that are slightly different depths (planes) may develop cracks, linking them together
• Interconnecting cracks btw the blisters have stair step appearance; “stepwise cracking” (Fig 5-23, 5-24, 5-25)

• Stress Oriented Hydrogen Induced Cracking (SOHIC)

• Potentially more damaging cracking than HIC
• Appears as arrays of cracks stacked on top of each other
• Result in through-thickness crack, perpendicular to surface
• Driven by high levels of stress (residual or applied) or notch-like discontinuities (eg shallow sulfide stress cracks)
• Usually appear in base metal adjacent to weld HAZ, initiated from HIC damage or other cracks or defects including sulfide stress
cracks (Fig 5-26, 5-27)

• Sulfide Stress Corrosion Cracking (SSC)

• Cracking of metal under combined action of tensile stress & corrosion in the presence of water and H2S
• A form of hydrogen stress cracking  resulting from absorption of atomic hydrogen, produced by sulfide corrosion process on
metal surface
• Initiate on the steels surface in highly localized zones of high hardness in the weld metal & HAZ
• Where are zones of high hardness and why, how?
• Weld cover passes and attachment welds which are not tempered (softened) by subsequent passes
• PWHT  reduce hardness & residual stresses
• High strength steels are also at risk of SCC, but limited to refining industry (Fig 5-28, 5-29)
• Some CS have residual elements that form hard areas in the HAZ that will not temper at normal stress relieving temp  use
preheat to minimize this problem

Affected • CS
materials • Low alloy steels

Internal
 Refining Industry - Environment-Assisted Cracking

Wet H2S Damage (Blistering/HIC/SOHIC/SSC)

Critical • Variables that affect and differentiate various forms of wet H2S damage are:
factors • Environmental conditions (pH, H2S level, contaminants, temp)
• Material properties (hardness, microstructure, strength)
• Tensile stress level (applied or residual)
• pH
• Hydrogen permeation or diffusion rates : minimal at pH 7| ↑ at both higher & lower pH
• Hydrogen cyanide (HCN) in water phase ,↑ permeation in alkaline (high pH) sour water
• Conditions known to promote the damages:
• Containing free water (in liquid phase)
• >50 wppm dissolved H2S in the free water, or
• Free water with pH <4 & some dissolved H2S present, or
• Free water with pH >7.6 & 20 wppm dissolved HCN in the water & some dissolved H2S present, or
• >0.0003 MPa (0.05 psia) partial pressure of H2S in the gas phase
• ↑ level of ammonia  may push pH higher into cracking range

• H2S
• H2S partial pressure ↑  Hydrogen permeation ↑ : why : concurrent ↑ in H2S concentration in the water phase
• Concentration of H2S in water phase where wet H2S damage = 50 wppm
• For steels with tensile strength > 90ksi / steels with localized zones of weld or weld HAZ hardness > 237 HB  SSC risk ↑ with H2S
partial pressure ↑ above 0.05psi (0.0003 mpa)
• Temperature
• Blistering, HIC, SOHIC  temp btw ambient & 150C or higher
• SSC  Temp < 82C
• Hardness
• Primarily an issue with SSC
• NACE RP0472  low-strength CS used in refinery = weld hardness <200 HB
• These steels are not generally at risk to SSC, UNLESS localized zones of hardness >237 HB are present
• Steelmaking
• Blistering & HIC  affected by inclusions, laminations, & other internal discontinuities (sites for diffusing hydrogen to accumulate),
or so-called “dirty” steels
• NACE Publication 8X194  outlines requirement to produce HIC resistant steels
• PWHT
• PWHT will NOT prevent blistering and HIC
• PWHT is effective in preventing/eliminating SSC by reduction of both hardness & residual stress
• PWHT is somewhat effective in reducing SOHIC damage (reduce localized stresses)

Internal
 Refining Industry - Environment-Assisted Cracking

Wet H2S Damage (Blistering/HIC/SOHIC/SSC)

Affected • Throughout refinery wherever there is a wet H2S environment • SSC found in
units / • In hydroprocessing units, if ↑ ammonium bisulfide >2%  ↑ • Hard weld
equipment potential of blistering, HIC, SOHIC • HAZ
• Cyanides significantly ↑ probability & severity of blistering, HIC & • High strength components (bolts, relief valve springs, 400
SOHIC damage Series SS valve trim, compressor shafts, sleeves & springs)
• In pressure-containing equipment, SOHIC & SSC most often found
in weldments
Appearance • As per figures
or
morphology
of damage
Prevention / • Effective barriers  alloy cladding & coatings • To prevent SSC, we can limit hardness of welds & HAZ to 200 HB
Mitigation • Process changes that affect pH of water phase , ammonia & max via
cyanide concentration • Preheat
• Utilize wash water injection to dilute HCN concentration • PWHT
in FCC gas plants • Weld procedures
• Inject dilute ammonium polysulfides to convert cyanides • Control of carbon equivalents
to harmless thiocyanates • Allow small zones of hardness up to 22 HRC  Refer
• Choose HIC-resistant steels  NACE Publication 8X194 NACE RP0472
• To minimize SOHIC, do PWHT  reduce residual stresses & • Use specialized corrosion inhibitors
strength levels
Inspection & • Evaluate process conditions
monitoring • Perform field sampling of free water phase
• Focus on weld seams and nozzles
• Perform detection & repair per NACE RP0296
• Crack detection by WFMT, EC, RT or ACFM
• UT (including external SWUT)
• To determine crack depth  grinding or thermal arc gouging
• Monitor crack growth using AET
Related • SSC is a form of hydrogen stress cracking (hydrogen embrittlement)
mechanisms • Amine cracking & carbonate cracking can also occur in wet H2S environments, may be similar in appearance, and are sometimes confused
with various forms of wet H2S damage.

Internal
 Refining Industry - Environment-Assisted Cracking

Wet H2S Damage (Blistering/HIC/SOHIC/SSC)

Internal
 Refining Industry - Environment-Assisted Cracking

Wet H2S Damage (Blistering/HIC/SOHIC/SSC)

Internal
 High Temperature Corrosion (204degC)

Internal
 High Temperature Corrosion (204degC)

Oxidation
Description • Oxygen reacts with CS & other alloys at high temp  metal converts to oxide scale
of damage
Affected • All iron based materials
materials • All 300 Series SS, 400 Series SS & nickel-base alloys
Critical • Metal temperature
factors • Oxidation of CS  significant above 538degC
• Temp ↑  rates of metal loss ↑
• Alloy composition
• Resistance of CS & other alloy steels depends on CHROMIUM content
• ↑ chromium  more protective oxide scale
Affected • Fired heaters
units / • Other combustion equipment, piping
equipment • Equipment operating in high temp when metal temp > 538degC
Appearance • Most alloys • 300 Series SS & nickel alloys
or • General thinning • Very thin dark scale
morphology • Component covered with oxide scale (Fig 4-62, 4-63, 4-
of damage 64)
Prevention / • Use more resistant alloy
Mitigation • Chromium is the primary alloying element that affects resistance to oxidation
• Silicon & aluminium are effective but will affect mechanical properties (normally in heater supports, burner tips, combustion components)
Inspection & • Process conditions to monitor high temp trending
monitoring • Monitor temp using tubeskin thermocouples and/or infrared thermography
• UT  measure loss in thickness
Related
mechanisms

Internal
 High Temperature Corrosion (204degC)

Oxidation

Internal
 High Temperature Corrosion (204degC)

Oxidation

Internal
 High Temperature Corrosion (204degC)

Sulfidation
Description • Corrosion of CS & other alloys • Hydrogen presence accelerates corrosion
of damage • Steel reacts with sulfur compounds in high temp environments
Affected • All iron based materials (includes CS, low alloy steels, 300 Series SS, 400 Series SS)
materials • Nickel-based alloys affected at varying degrees, depending on composition especially chromium content
• Copper-based alloys for sulfide at lower temp than CS
Critical • Alloy composition
factors • Risk of an alloy to sulfidation is determined by its ability to form PROTECTIVE SULFIDE SCALES
• Sulfide scale on the component’s surface give varying degree of protection, depending on alloy & process stream severity
• Chromium content affect resistance
• ↑ chromium content  significantly ↑ resistance
• 300 Series SS (304, 316, 321, 347)  highly resistant in most refining process environments
• Nickel-based alloys & SS have similar levels of chromium  provide similar resistance
• Temperature
• Usually begins at metal temp >260C
• Typical effects of increasing temp, chromium content, sulfur content on metal loss (Fig 4-65, 4-66)
• Concentration of corrosive sulfur compounds
• Crude oils, coal & other HC streams contain sulfur at various concentrations
• Total sulfur is made up of many different sulfur-containing compounds
• Sulfidation primarily caused by H2S & other reactive sulfur species  due to thermal decomposition of sulfur compounds at high
temp
• Some sulfur compounds react more readily to form H2S  it can be misleading to predict corrosion rates based on weight %
sulfur alone
Affected
units /
equipment
Appearance
or
morphology
of damage
Prevention /
Mitigation
Inspection &
monitoring
Related
mechanisms

Internal