Damage Mechanism in Refinery Area

Damage Mechanism in Refinery
based on API RP 571, 2nd edition 2011
Pertamina RU IV
Cilacap, 8-9 February 2019
Subject to discuss
1. Introduction to Damage Mechanism

2. Mechanical / Metallurgical Degradation
3. Loss of Wall Thickness
4. High Temperature (>400ºF)
5. Environmentally Assisted Cracking
6. Refinery Chemical Acid/Alkaline
Introduction to Damage Mechanism
Basic Structure of API RP 571
Mechanical / Metallurgical Degradation
1.Loss of Wall Thickness
Damage
1.High Temperature (>400ºF)
Mechanism
1.Environmentally Assisted Cracking
1.Refinery Chemical Acid/Alkaline
Acknowledgement: API RP 571, 2011 & www.matthews-training.co.uk

How DM is Explained by API RP 571
Description of Prevention / Inspection and

DM Mitigation Monitoring
Affected Damage
References
Material Morphology
Critical Factor
Affected
Controlling
Equipment
DM
Acknowledgement: API RP 571, 2011

API RP 571 Link with other Code & Standards
API /ASME
Construction API RP 579 FFS
API RP 571 DM
code, e.g. ASME Assessment
VIII/B31.
• New Equipment (no • DM affect the • To determine if the

DM) equipment in service equipment is still
• Start goes into • If equipment is safe to use
service damaged beyond
the limit

Mechanical Properties Background
Acknowledgement: www.matthews-training.co.uk
Mechanical Properties Background
Ductility ≠ Toughness
Ductility is the ability of metal grains to slide and deform
While
Toughness is the ability to prevent small cracks propagates
when metal is deforming.
Mechanical Properties
Type of Damage Mechanism
Corrosion Non- Corrosion

Mechanism Mechanism
 Erosion
 Brittle Fracture
 Creep
 Mechanical Fatigue
 Reheat Cracking
Factor That Influence the Corrosion
Temperature
Increases Energy & molecular
movement
Stress Chemical (pH)

Tensile, fatigue, shear,
Corrosion Encourage ion metal
etc. Damage Rate and Area reaction
Presence of O2
Encourage oxide formation
Basic Structure of API RP 571
Mechanical / Metallurgical Not corrosion, failure mode

Degradation by cracking & wakening
Corrosion, mostly by
1.Loss of Wall Thickness oxidation, T < 400F, various
corrosion morphology
Damage T > 400F, serious attack

1.High Temperature when chemical is combined.
Mechanism Creep (excluded)
1.Environmentally Assisted Process environment, mostly

preceded by Cracking.
Cracking Chemical attack
1.Refinery Chemical Susceptible in Refinery

(downstream).
Acid/Alkaline Acid / alkaline environment.

DM Group I
1. Graphitization 11. Steam Blanketing
2. Softening (Spheroidization) 12. Dissimilar Metal Weld (DMW)
3. Temper Embrittlement Cracking
4. Strain Aging 13. Thermal Shock
5. 885 F (475ºC) Embrittlement 14. Erosion/Erosion – Corrosion
6. Sigma Phase Embrittlement 15. Cavitation
7. Brittle Fracture 16. Mechanical Fatigue
8. Creep and Stress Rupture 17. Vibration-Induced Fatigue
9. Thermal Fatigue 18. Refractory Degradation
10. Short Term Overheating – Stress 19. Reheat Cracking
Rupture 20. Gaseous Oxygen-Enhanced Ignition
and Combustion
Graphitization
Decomposition carbide to graphite
Description of
nodules causing loss in strength,
Damage
ductility and/or creep resistance.
800°F - 1100°F;
Critical Factors
Weldments, coarse pearlitic
Affected
Some grades of CS and 0.5Mo steels
Materials
Affected Hot wall in FCC, catalytic reforming,

Equipment coker unit.
Not visible
Morphology Micro-fissures cracks (by
metallography)
Prevention Addition of 0.7% Cr
Inspection Full thickness sample metallography

Softening (Spheroidization)
Carbide phase is unstable and

Description of agglomerate to spheroidal form
Damage causing loss in strength and/or creep
resistance.
850°F - 1400°F,
Critical Factors Fined grain / Si-killed are more
resistant.
Affected
CS and low alloys
Materials
Hot wall in FCC, catalytic reforming,

Affected
coker unit.
Equipment
Fired heater tubes.
Morphology Not visible (unless with metallography)
Prevention Minimize exposure to elevated temps
Field metallography or removal of

Inspection
samples

Graphitization
vs
Spheroidization

Brittle Fracture
Cracking with little plastic
Description of deformation due to operation
Damage below the ductile-to-brittle
transition temperature for material
Carbon and chromium content

(embrittling phase)
Hardness (inadequate PWHT)
Critical Factors Thick wall
Flaws
Residual stress
Affected
CS and low alloy steel. 400 SS
Materials
Thick wall operates at elevated

Affected temp.
Equipment Auto refrigeration event of
equipment.
Single or multiple cracking with flat

Morphology
fracture faces
Material design for low

Prevention temperature, PWHT, warm pre
stress hydrotest.

Temper Embrittlement
Reduction in toughness. Upward
Description of shift in the ductile-to-brittle
Damage transition temperature. (by Charpy
impact testing)
650°F - 1100°F;
900°F (heat treatment), severe in
Critical Factors
long-term exposure at 850°F.
Crack flaws
Affected Primarily 2.25Cr; Older 2.25Cr manuf.

Materials prior to 1972 particularly susceptible
hydro processing units,

Affected
reactors, hot feed/effluent
Equipment
exchanger, and hot HP separators
Not visible.
Morphology Brittle fracture, identified by impact
test.
Pressurization sequence - MPT of

350°F for older steels and 150°F
Prevention newer; Heat treat to 1150°F and cool
rapidly for temporary reverse; Limit J
and X factors.
Impact test sample blocks from

Inspection
original heat

885°F Embrittlement
Loss in toughness due to a

Description of
metallurgical change that occurs in
Damage
alloys containing a ferrite phase
885°F (475°C); 600°F - 1000°F

Critical Factors Chromium content, ferrite phase.
Higher tempering temperature.
Affected Alloys containing a ferrite phase; 400

Materials SS and Duplex SS
Affected Tower - internal trays at FCC, crude,

Equipment vacuum and coker units.
Not visible (unless metallography)

Morphology
Identified by increase in hardness.
Use low ferrite or non-ferritic alloys;

Prevention
Heat treat to 1100°F and cool rapidly
Impact/bend test samples; Cracking

Inspection during TA or when below 200°F;
Increase in hardness.

Sigma Phase Embrittlement
A brittle sigma phase formation
Description of
resulting in a loss of fracture
Damage
toughness.
1000°F - 1750°F, exposure time,

Alloy composition,
Critical Factors
Ferrite phase, austenite more
severe.
Affected Ferritic, martensitic, austenitic, and

Materials duplex SS
SS cyclones, piping / valves in high

Affected
temperature FCC Regenerator
Equipment
service.
Not visible (unless metallography)
Damage appears in cracking at
Morphology
welds or high restraint.
SS with sigma may have lack of

toughness below 500°F; Minimize
Prevention weld metal ferrite content; Solution
anneal at 1950°F and water quench
to reverse.
Testing of samples; Cracking during

Inspection
t/a or when below 500°F
Creep and Stress Rupture
Continuous deformation eventually
Description of leads to rupture at depends on high
Damage temperature and load stress below
yield strength.
Threshold Temp:
C.S. --> 700ºF
C-1/2 Mo --> 750ºF
1.25Cr thru 9Cr --> 800ºF
Critical Factors 304H --> 900ºF
347H --> 1000ºF
Grain size. Single is best. Fine is

better, coarse is worst.
Affected
All metals and alloys
Materials
Hot-wall catalytic reforming reactors
Affected
and furnace tubes, FCC fractionator
Equipment
and regenerator.
Identified by SEM as creep voids
Morphology Noticeable deformation exhibit
bulging before fracture.
Minimize temperatures; Higher
Prevention PWHT may help; Minimize hot spots
in heaters
Combination of techniques; Tubes

Inspection
bulging, sagging, diametric growth
Thermal Fatigue
Cyclic stresses fatigue caused by
variations in temperature.
Description of
Damage is in the form of cracking
Damage
where relative movement or
differential expansion under
repeated thermal cycling.
Temp swings exceeding 200°F

Critical Factors
Notches/Tip flaws.
Affected
All materials of construction
Materials
hydrogen mix points in

Affected
hydro processing units, coke drum
Equipment
shells, de-superheating component.
Crack at surface. Transverse and

Morphology
transannular.
Design and operation; Liner to

Prevention prevent cold liquid from contacting
hot surface
Inspection VT, MT/PT, SWUT for cracking

Short Term Overheating – Stress Rupture
Permanent deformation occurring at
relatively low stress levels as a result
Description of
of localized overheating. This usually
Damage
results in bulging and eventually
failure by stress rupture.
Local overheating above design

Critical Factors temperature.
Flame impingement.
Affected All fired heater tube materials and

Materials common materials of construction
Affected Boiler/fired heater tube. Hydro

Equipment processing reactor.
Localized deformation / bulging.

Morphology
Fish-mouth failure
Minimize temperature excursions;

Prevention
Burner management
Visual; IR monitoring; Tubeskin

Inspection
thermocouples

Steam Blanketing
Tube rupture due to Departure From

Description of
Nucleate Boiling (DNB) - steam
Damage
blanket forms.
Heat flux & fluid flow, overheating,

Critical Factors
flame impingement.,
Affected
CS and low alloys
Materials
Affected Steam-generating units, e.g. at sulfur

Equipment plant, hydrogen reformers, FCC
Open burst with fracture edges (knife

Morphology
edge). Elongation of grain structure
Prevention Burner management
Visual for bulging on tubes and

Inspection
burners

Dissimilar Metal Weld (DMW) Cracking
Cracking of dissimilar metal welds
occurs in the ferritic (carbon steel or
Description of
low alloy steel) side of a weld
Damage
between an austenitic (300 Series SS
or Nickel base alloy)
Filler material
Critical Factors Different thermal expansion coeff.
> 510°F
Widely differing thermal expansion

Affected
coefficients; Most common CS to
Materials
Austenitic SS
Affected Welds at hydro processing reactors,

Equipment hydrogen reformer, FCC reactors
Crack at weld / HAZ of ferritic

Morphology
materials
Ni based fillers; 300 SS rods used in

Prevention low temp location only; Pup piece
with intermediate coefficient
Visual and MT/PT for OD cracks; UT

Inspection
for ID cracks

Thermal Shock
Thermal shock occur when
high and non-uniform thermal
stresses develop over a
Description of
relatively short time in a piece
Damage
of equipment due to
differential expansion or
contraction.
Significant Temperature
Differentials.
Critical Factors Coefficient of thermal
expansion
Temp. cyclic
Affected Materials All metals and alloys
FCC, cokers, catalytic

Affected Equipment reforming.
Accelerate cooling procedure
Surface initiating cracks

Morphology
“Craze”
Minimize flow interruptions,

severe restraint, rain/fire water
Prevention
deluge; Review injection
points; Thermal sleeves
Highly localized; MT/PT to

Inspection
confirm cracking only

Erosion / Erosion–Corrosion
Accelerated mechanical removal of
surface impact from solids, liquids,
vapor etc.
Description of
Erosion-corrosion is a damage that
Damage
occurs when corrosion contributes to
erosion by removing protective films
or scales, or by exposing the metal
surface.
velocity and concentration of

Critical Factors
impacting medium
Affected
All metals, alloys and refractories
Materials
Equipment exposed to moving

Affected
fluids/catalyst. FCC, Hydro
Equipment
processing reactor, etc.
localized loss: pits, grooves, waves,

Morphology
rounded holes and valleys
Design; Erosion - harder alloys;

Prevention Corrosion - corrosion resistant alloys;
Impingement plates; Tube ferrules
VT, UT, RT; Corrosion coupons; IR

Inspection
scans for refractory
Cavitation
Form of erosion caused by
the formation and
Description of
instantaneous collapse of
Damage
innumerable tiny vapor
bubbles.
Inadequate NPSH
Critical Factors Temps approaching the
liquid boiling point
Most common materials of

Affected Materials
construction
pump casings, pump

Affected Equipment
impellers, orifice downstream
sharp-edged pitting, gouged

Morphology
rotational
Mechanical, design, or
operational change;
Prevention Sufficient NPSH; Streamline
flow; Remove air; Decrease
velocities; Fluid additives
Acoustic monitoring; Pumps
may sound like pebbles
Inspection
being thrashed around; VT,
UT, RT for loss of thickness

Mechanical Fatigue
Cracking degradation that
occurs when is exposed to
Description of cyclical stresses for an
Damage extended period, often
resulting in sudden,
unexpected failure.
Geometry, stress level,

Critical Factors number of cycles, and
material properties
All alloys; Stress levels and

Affected Materials number of cycles to failure
vary by material
Coke drum, auxiliary boiler,

Affected Equipment
SBF, rotating equipment.
Morphology Clam shell or beach marks
Good design; Material

Prevention selection; Minimize stress
risers
MT, PT, SWUT for cracks;

Inspection
Vibration monitoring

Vibration-Induced Fatigue
Cracks that produced as the
Description of result of dynamic loading due
Damage to vibration, water hammer, or
unstable fluid flow.
Amplitude and frequency of

vibration.
Critical Factors
Lack of support/ stiffening.
Stress raisers
Affected Materials All engineering materials
SBF, Relieve valve system, HE

Affected Equipment
tubes (vortex shedding)
Crack initiates at high stress

Morphology
point / discontinuity.
Design; Supports and

vibration dampeners;
Prevention
Stiffeners on small bore;
Branch sizing
Visual/Audible signs of
Inspection
vibration

Refractory Degradation
Thermal insulating and refractories
forms of mechanical damage
Description of cracking, spalling and erosion as well
Damage as corrosion due to oxidation,
sulfidation and other high
temperature mechanisms.
Critical Factors Selection, design and installation.
Affected
Refractory materials
Materials
Affected FCC reactor regenerators, fluid

Equipment cokers, thermal reactors.
cracking, spalling or lift-off from the

Morphology
substrate
Prevention Selection; Design; Installation
Inspection VT during shutdown; IR online

Reheat Cracking
Cracking of a metal due to stress
Description of relaxation during Post Weld Heat
Damage Treatment (PWHT) or in service at
elevated temperatures.
During PWHT or at elevated temps >

Critical Factors 750 F.
Heavy wall section
low alloys, 300 SS, and Ni base

Affected
alloys; High Strength Low Alloys
Materials
(HSLA)
Affected Heavy wall vessels in area of high

Equipment restraint.
Intergranular, surface breaking.

Morphology HAZ and initiate of stress
concentration.
Joint configurations in heavy walls;

Prevention
Minimize stress risers
UT and MT/PT for surface cracks; UT

Inspection
for embedded cracks

DM related with Mechanical / Metallography
[High Temp. and Exposure]
DM Group II
Uniform or Localized Loss of Thickness
Uniform or Localized Loss of Thickness
1. Galvanic Corrosion
2. Atmospheric Corrosion
3. Corrosion Under Insulation (CUI)
4. Cooling Water Corrosion
5. Boiler Water Condensate Corrosion
6. CO2 Corrosion
7. Flue-Gas Dew-Point Corrosion
8. Microbiologically Induced Corrosion (MIC)
9. Soil Corrosion
10. Caustic Corrosion
11. Dealloying
12. Graphitic Corrosion
Galvanic Corrosion
Corrosion at the junction of
dissimilar metals in a suitable
Description of
electrolyte, such as a moist or
Damage
aqueous environment, or soils
containing moisture.
Presence of electrolyte, anode-

Critical Factors
cathode, electrical connection.
All metals with the exception of most

Affected
noble metals; SEE Table 4-4 for
Materials
Galvanic Series
Affected Buried pipe, HE with different

Equipment tubesheet/baffles materials.
General loss or local (crevice, groove,

Morphology
pitting)
Design; Differing alloys not in

Prevention
intimate contact; Coatings
Inspection Visual and UT Thickness

Atmospheric Corrosion
Corrosion that occurs from moisture
Description of
associated with atmospheric
Damage
conditions.
Environment (marine, industrial, etc.)

Corrosion rates increase with temp
Critical Factors
up to about 250°F.
Chloride, H2S from cooling tower
Affected
CS, low alloys, and copper alloyed Al
Materials
Affected Poor coating condition, mothballed

Equipment equipment, etc.
General or localized depends of

Morphology
moisture is trapped
Prevention Surface prep and proper coating
Inspection VT and UT

Corrosion Under Insulation (CUI)
Corrosion of piping, pressure vessels
Description of and structural components resulting
Damage from water trapped under insulation
or fireproofing.
More severe 212°F - 250°F for CS,

Critical Factors Insulation design and contaminants
(Cl, marine, etc.)
Affected
CS, low alloys, 300 SS and duplex SS
Materials
Affected
All insulated piping / equipment
Equipment
CS localized, SS tend to SCC if

Morphology
chloride is present.
Selection of insulation type; Maintain

Prevention
coatings and insulation
Inspection Strip insulation; VT, UT, IR, etc.

Cooling Water Corrosion
General or localized corrosion of
carbon steels and other metals
Description of
caused by dissolved salts, gases,
Damage
organic compounds or
microbiological activity.
Process side > 140°F; Brackish and

Critical Factors
salt water outlet > 115°F
Affected CS, all grades of SS, copper, Al,

Materials titanium and Ni base alloys
Affected Water cooled heat exchanger and

Equipment cooling towers
General corr., pitting, MIC, SCC &

Morphology
fouling.
Design process inlet < 135°F;

Operation; Chemical treatment;
Prevention
Maintain water velocities; avoid ERW
tubes
pH; Oxygen content; Outlet temps;

Inspection
EC/IRIS tubes
Acknowledgement: API RP 571

Boiler Water Condensate Corrosion
General corrosion and pitting in the

Description of
boiler system and condensate return
Damage
piping.
Dissolved gases, O2, CO2.

Critical Factors
pH, Tempe., quality of feed water.
Affected Primarily CS; Some low alloy, 300 SS

Materials and copper based alloys
Affected Deaerating equipment, feedwater

Equipment lines, steam generation system.
Morphology Pitting damage.
Oxygen scavenging treatment;

Prevention
Amine inhibitor treatment
Water analysis; Deaerator cracking

Inspection
WFMT

CO2 Corrosion
Carbon dioxide (CO2) corrosion
Description of
results when CO2 dissolves in water
Damage
to form carbonic acid (H2CO3).
Partial Pressure of CO2, pH &

Critical Factors
Temperature up to dew point.
Affected
CS and low alloys
Materials
Boiler feed water, condensate

Affected
system. Overhead system of CO2
Equipment
removal system.
Morphology General & localized (pitting)
Cr > 12% (SS); Corrosion inhibitors;

Increase pH > 6; Operation
Prevention
problems; 400 SS and Duplex SS
resistant; Water analysis
Inspection VT, UT, RT

Flue-Gas Dew-Point Corrosion
Flue gas condense to form sulfurous
Description of acid, sulfuric acid and hydrochloric
Damage acid which can lead to severe
corrosion.
Sulfuric acid dewpoint < 280°F;

Critical Factors Hydrochloric acid dewpoint < 130°F;
pH < 6
Affected
CS, low alloys and 300 SS
Materials
Affected Fired process heater that burn fuels

Equipment contain sulfur.
Morphology Shallow pits, SCC for 300 series
Maintain temps > 280°F; Avoid 300

Prevention SS if chlorides present; Soda ash
wash to neutralize the acids
Inspection UT for wall loss; VT and PT for SCC

Microbiologically Induced Corrosion
(MIC)
A form of corrosion caused by living
organisms such as bacteria, algae or
Description of
fungi. It is often associated with the
Damage
presence of tubercles or slimy
organic substances.
Aqueous environment, low flow,
Critical Factors organism/ inorganic substance.
0°F to 235°F; pH range 0 - 12 (Any)
Affected Most common materials of

Materials construction
Affected Often in heat exchanger, bottom

Equipment water of storage tanks, low flow.
Localized pitting under deposits.

Morphology
Cup-shaped pits.
Treat water with biocides; Maintain

Prevention flow velocities; Empty hydrotest
water; Maintain coatings
VT; Measure biocide residual;

Inspection Operating conditions indicate
fouling; Foul smelling water

Soil Corrosion
The deterioration of metals exposed
Description of
to soils is referred to as soil
Damage
corrosion.
Operating temperature, moisture,

Critical Factors oxygen availability, soil resistivity,
coating condition.
Affected Carbon steel, cast iron, and ductile

Materials iron
Affected Underground piping, buried tanks,

Equipment bottom of AST
Morphology Localized pitting.
Most effective coatings and cathodic

Prevention protection; Special backfill may help
to lesser degree
Structure to soil potential; Soil

Inspection resistivity; VT, guided UT, Pressure
testing

Caustic Corrosion
Localized corrosion due to the
concentration of caustic or alkaline
Description of
salts that usually occurs under
Damage
evaporative or high heat transfer
conditions.
High solution strength caustic

Critical Factors general corrosion of CS above 175°F
and very high CR rates above 200°F.
Affected
Primarily CS, low alloys and 300 SS
Materials
Boiler / steam generating HE

Affected
Caustic injected to crude unit / sulfur
Equipment
compound removal
Morphology Localized
Design; Adequate water flooding;

Prevention Burner management; Dilution of
caustic
UT Scans, RT, Injection points,

Inspection Boroscope steam generating
equipment

Dealloying
Dealloying is a selective corrosion
mechanism in which one or more
Description of constituents of an alloy are
Damage preferentially attacked leaving a
lower density (de-alloyed) often
porous structure.
Temperature, degree of aeration, pH

Critical Factors
and exposure time.
Affected Primarily copper alloys as well as

Materials Alloy 400 and cast iron
U/G cast iron piping, HE tubing

Affected (brass, Al brass)
Equipment Boiler feed water system (bronze
pump)
Morphology Color change (corroded)
Difficult to predict; Addition of

Prevention alloying elements may help; CP or
coatings may help
VT (may change color but may
require scale removal),
Inspection
Metallography, Loss of "metallic
ring"

Graphitic Corrosion
Graphitic corrosion is a form of
Description of dealloying in which the iron matrix is
Damagelo corroded, leaving corrosion products
and porous graphite.
Low pH
Stagnant condition
Critical Factors
< 200°F in the presence of moisture
or an aqueous phase
Primarily gray cast iron, but also

Affected nodular and malleable cast irons
Materials which tend to crumble when
attacked
Affected U/G piping, boiler feed water

Equipment equipment.
Morphology Localized area of damage.
Difficult to predict; Internal

coatings/cement linings for internal
Prevention
graphitic corrosion; external coatings
or CP in corrosive soils
Loss of "metallic ring"; Reduction in

Inspection
hardness

DM Group III
High Temperature Corrosion
[>400ºF (204ºC)]
High Temperature Corrosion [>400ºF (204ºC)]
1. Oxidation
2. Sulfidation
3. Carburization
4. Decarburization
5. Metal Dusting
6. Fuel Ash Corrosion
7. Nitriding

Oxidation
Oxygen reacts with carbon steel and
Description of
other alloys at high temperature
Damage
converting the metal to oxide scale.
Oxidation of CS significant > 1000°F;

300 Series SS susceptible to scaling
Critical Factors > 1500°F.
SEE Table 4-6 for CR at elev.
Temps
CS and low alloys; All 300 SS, 400 SS

Affected
and Ni base alloys oxidize to varying
Materials
degrees
Affected
Fired heater and boiler.
Equipment
Morphology General thinning with oxide scaling
Upgrade alloy; Addition of Cr

Prevention primary element for oxidation
resistance
Monitor process conditions and

Inspection
temperatures; UT for thickness loss

Sulfidation
Corrosion of carbon steel and other
Description of alloys resulting from their reaction
Damage with sulfur compounds in high
temperature environments.
Hydrogen content
Critical Factors
> 500°F
CS, low alloys, 300 SS and 400 SS; Ni

Affected base alloys to varying degrees
Materials depending on Cr content; Copper
base alloys at lower temps than CS
High temp sulfur containing stream

Affected
Crude, FCC, coker, vacuum, vis-
Equipment
breaker, hydro processing unit.
Uniform thinning, deposit thick/thin

Morphology
scales.
Upgrade to higher Cr; Al diffusion

Prevention treatment of low alloys may reduce
but not completely protect
Monitor process conditions and

Inspection temperatures; UT for thickness loss;
Proactive and retroactive PMI

Carburization
Carbon is absorbed into a material at
Description of elevated temperature while in
Damage contact with a carbonaceous material
or carburizing environment.
carburizing environment (HC, coke,

Critical Factors gas rich CO)
> 1100°F
CS and low alloys, 300 SS and 400
Affected SS, cast SS, Ni base alloys with
Materials significant Fe content and HK/HP
alloys
Affected Fired heater tube, coke deposits,

Equipment heater tube catalytic reformer.
Hardness & loss ductility. Increase in

Morphology
level of ferromagnetism.
Alloy selection (Si & Al oxidizers);

Prevention Lower temperatures and higher
oxygen/sulfur partial pressures.
Hardness/Field metallography if
Inspection process side accessible; RT, UT, MT
for cracking in advanced stages

Decarburization
A condition where steel loses
Description of strength due the removal of carbon
Damage and carbides leaving only an iron
matrix
Exposure time
Critical Factors Exposed to low carbon gas phase
Elevated temperatures
Affected
CS and low alloys
Materials
Hot hydrogen service in hydro

Affected
processing or catalytic reforming
Equipment
unit.
Decarburized layer free of carbide

Morphology
(by metallography)
Control chemistry of gas phase; Cr

Prevention
and Mo form more stable carbides
Field metallography; Hardness tests

Inspection
for softening

Metal Dusting
Metal dusting is form of
carburization resulting in accelerated
Description of
localized pitting. Pits usually form on
Damage
the surface and may contain soot or
graphite dust.
Carburizing gases and/or process

streams containing carbon and
Critical Factors
hydrogen.
900°F - 1500°F
Affected All; No known alloy immune under all

Materials conditions
Fired heater tubes, catalytic

Affected
reforming unit heater tubes, coker
Equipment
heaters.
Uniform wastage, small pits filled
Morphology with metal oxide and carbide.
SS local and deep round pits.
Protective layer of sulfur (usually as
Prevention H2S); Material selection for specific
application; Al diffusion treatment
Compression wave UT for heater

Inspection tubes; RT for pitting/thinning; VT if ID
is accessible

Fuel Ash Corrosion
a) Accelerated high
temperature metal
wastage to melted fuels
contaminant
Description of
b) Sulfur, sodium, potassium
Damage
and/or vanadium.
c) The resulting molten salts
dissolve the surface oxide
leads further oxidation
Oil ash - 1000°F;

Critical Factors Water wall corrosion - 700°F;
Coal ash - 1030°F to 1130°F
All conventional alloys for

Affected Materials
process heaters and boilers;
Affected Equipment Fired heater, contaminant fuel
Metal loss, crack, slush

Morphology
(waterwall), glassy slag (coal)
Blend or change fuel source;

Burner design/management;
Prevention
Low excess oxygen; Alloy
upgrade to 50Cr-50Ni
Inspection VT; UT for loss of thickness

DM Group IV
Environment – Assisted Cracking
Environment – Assisted Cracking
1. Chloride Stress Corrosion Cracking

2. Corrosion Fatigue
3. Caustic Stress Corrosion Cracking (Caustic Embrittlement)
4. Ammonia Stress Corrosion Cracking
5. Liquid Metal Embrittlement (LME)
6. Hydrogen Embrittlement (HE)
7. Ethanol Stress Corrosion Cracking
8. Sulfate Stress Corrosion Cracking
Environment – Assisted Cracking – Overall Picture
image courtesy: www.matthews-training.co.uk

Chloride Stress Corrosion Cracking (Cl-SCC)
Surface cracks under the combined
Description of action of tensile stress, temperature
Damage and an aqueous chloride
environment.
Chloride content, pH, stress, oxygen

Critical Factors
temp. (> 140°F)
300 SS; Ni 8% - 12% most

Affected
susceptible; Ni > 35% highly
Materials
resistant, Ni > 45% nearly immune
Affected Any unit of SS equipment with

Equipment Chloride contaminant.
Morphology Surface crack, branches craze.
Material selection; Low chloride

water for hydrotest; Coatings under
Prevention
insulation; Avoid designs where
chlorides can concentrate
VT in some cases, PT (surface prep

Inspection
may be necessary), ECT, UT

Caustic Stress Corrosion Cracking (Caustic Embrittlement)
Surface-initiated cracks that occur
Description of in piping and equipment exposed
Damage to caustic, primarily adjacent to
non-PWHT’d welds.
Caustic (KOH, NaOH) strength,

Critical Factors
Metal Temperature, Stress Level
Affected CS, low alloys and 300 SS; Ni base

Materials alloys more resistant.
Equipment that handle caustic at

Affected
H2S and mercaptan removal unit.
Equipment
Alkylation unit
Cracks propagates parallel to weld

Morphology
Spider web.
PWHT at 1150°F for CS; Alloy

upgrade to Ni based alloys;
Prevention Design/operation of injection
system; Water wash equipment
prior to steam out
WFMT, EC, RT, ACFM for crack
detection; PT not effective (tight,
Inspection
scale-filled cracks); SWUT for crack
depth

Ammonia Stress Corrosion Cracking
a) Aqueous streams containing
ammonia may cause Stress
Description of Corrosion Cracking (SCC) in
Damage some copper alloys.
b) Carbon steel is susceptible to
SCC in anhydrous ammonia.
Residual stress, pH, Ammonia

Critical Factors
content.
Copper alloys with aqueous

Affected ammonia and/or ammonium
Materials compounds;
CS in anhydrous ammonia
Affected Cu-Zn alloy tubes HE

Equipment CS containing ammonia (tank, pipe)
Surface break crack (Cu)

Morphology
Weldment intergranular crack (CS)
Copper - zinc content below 15%,

90- 10CuNi and 70-30CuNi nearly
immune, prevent ingress of air,
Prevention upgrade to 300 SS or Ni alloys; CS -
PWHT or addition water (0.2%), weld
< 225 BHN, prevent ingress of
oxygen
Copper - monitor pH, ECT or VT on

Inspection tubes for cracking; CS - WFMT, AET,
or External SWUT
Liquid Metal Embrittlement (LME)
a form of cracking that results when
certain molten metals come in
Description of
contact with specific alloys. Cracking
Damage
can be very sudden and brittle in
nature.
Specific combination of metals

Critical Factors
High tensile stress.
Affected
Many commonly used materials
Materials
Affected Refinery, mercury from oil vs Al

Equipment LNG, liquid mercury vs Al
Morphology Brittle crack, intergranular crack.
Keep metal with low melting point

Prevention away from other metal; Grind out
cracks not acceptable
MT or PT for cracks, RT for mercury

Inspection
deposits inside tubes

Hydrogen Embrittlement (HE)
A loss in ductility of high strength steels due to the
Description
penetration of atomic hydrogen can lead to brittle
of Damage
cracking.
• Hydrogen at critical concentration within steel

• Strength of steel
Critical
• Stress
Factors
H2 from welding, cleaning, high temp H2, H2S service,
CP
Affected CS, low alloys, 400 SS, Precipitation Hardenable SS,

Materials some high strength Ni base alloys.
Affected FCC, hydro processing, amine, sour service, HF

Equipment alkylation.
Sub surface crack

Morphology
Brittle fracture
Use lower strength steels; PWHT; Low hydrogen, dry

electrodes, and preheat for welding; Bake out at 400°F
Prevention
or higher; Controlled pressurization sequence;
Protective lining, SS cladding, or weld overlay
MT or PT for surface cracks; UT may be helpful; RT not

Inspection
sensitive enough

DM Group V
Refining Industry Damage Mechanisms
DM.V. Uniform or Localized Loss in Thickness Phenomena
1. Amine Corrosion
2. Ammonium Bisulfide Corrosion (Alkaline Sour Water)
3. Ammonium Chloride Corrosion
4. Hydrochloric Acid (HCl) Corrosion
5. High Temp H2/H2S Corrosion
6. Hydrofluoric (HF) Acid Corrosion
7. Naphthenic Acid Corrosion (NAC)
8. Phenol (Carbolic Acid) Corrosion
9. Phosphoric Acid Corrosion
10. Sour Water Corrosion (Acidic)
11. Sulfuric Acid Corrosion
12. Aqueous Organic Acid Corrosion
Amine Corrosion
Corrosion results from dissolved acid gases
Description (CO2 and H2S), amine degradation products,
of Damage Heat Stable Amine Salts (HSAS) and other
contaminants at amine treating process.
Critical Type of amine, amine concentration,

Factors contaminants, temperature and velocity.
Affected
Primarily CS; 300 SS highly resistant
Materials
Affected Amine treating unit. Amine regenerator and

Equipment reboiler. Rich amine side.
Morphology General or localized (under deposit)
Proper operation; Avoid build up of HSAS;

Design should control local pressure drop to
Prevention minimize flashing; Avoid oxygen in leakage;
Remove solids and hydrocarbons; Corrosion
inhibitors
VT and UT thickness internal; UT scans or

Inspection
profile RT for external; Corrosion coupons

Ammonium Chloride Corrosion
General or localized corrosion, often
pitting, normally occurring under
Description
ammonium chloride or amine salt
of Damage
deposits, often in the absence of a free
water phase.
Salt concentration, free water,

Critical
< 300°F; May corrode well above water
Factors
dewpoint of 300°F
All commonly used materials; Order of

Affected increasing resistance: CS, low alloys, 300
Materials SS, Alloys 400, duplex SS, 800, and 825,
Alloys 625 and C276 and titanium.
Crude tower overhead, reactor effluent
Affected
hydro processing, catalytic reforming,
Equipment
FCC fractionator overhead.
Morphology Corrosion underneath salts.
Pitting resistant alloys more have

Prevention improved resistance; Limit chlorides;
Water wash; Filming inhibitors
RT or UT Thickness; Monitor feed

Inspection streams; Corrosion coupons may be
helpful if salts deposit on the element

Hydrochloric Acid (HCl) Corrosion
Corrosion that associated with dew
point corrosion in which vapors
Description of
containing water and hydrogen
Damage
chloride condense in highly acidic –
hydrochloric acid (low pH)
HCl concentration, temperature, alloy

Critical Factors
composition.
Affected All common materials of

Materials construction
Affected Crude unit at tower overhead

Equipment Hydro processing at reactor effluent
General thinning, localized under

Morphology
deposit.
Upgrade CS to Ni base can help;

Remove chlorides (neutralize, water
Prevention
wash, absorb, etc.); Minimize
carryover of water and salts
AUT or RT for thickness; Corrosion

Inspection
coupons; Check pH

High Temp H2/H2S Corrosion
The presence of hydrogen in H2S-
containing hydrocarbon streams
Description of increases the severity of high
Damage temperature sulfide corrosion at
temperatures above about 500°F
(260°C).
High temp. > 500°F, hydrogen,

Critical Factors concentration of H2S and alloy
composition
Affected Order of increasing resistance: CS,

Materials low alloys, 400 SS, and 300 SS
Affected High temp. with H2/H2S, such as

Equipment Hydro processing unit
Morphology Uniform loss, scaling.
Use alloys with high chromium

Prevention content; 300 SS are highly resistant
at service temps
UT, VT and RT for thickness; Verify

Inspection operating temps; Check process H2S
levels periodically

Hydrofluoric (HF) Acid Corrosion
Corrosion by HF acid can result in high rates
Description of of general or localized corrosion and may be
Damage accompanied by hydrogen cracking,
blistering and/or HIC/SOHIC
HF concentration, allow composition, oxygen

contaminant.
Critical Factors
Increase with increasing temp; High CR rates
observed > 150°F
Low alloys, 300 SS and 400 SS are generally

Affected not suitable; CS, Cu-Ni alloys, Alloy 400, an
Materials other Ni base alloys have been used in some
applications
Affected
HF alkylation unit
Equipment
Localized
Morphology Corrosion may be accompanied by SCC and
blistering.
Monitor CS operating > 150°F for thickness;

Minimize water, oxygen, sulfur and other
Prevention contaminants in feed; Alloy 400 (solid or
clad) used to eliminate blistering/HIC/SOHIC.
PWHT to minimize possibility of SCC.
RT or UT Thickness; Monitor small bore

piping, flange face corrosion,
Inspection blistering/HIC/SOHIC
Naphthenic Acid Corrosion (NAC)
A form of high temperature
corrosion that occurs primarily in
Description of crude and vacuum units, and
Damage downstream units that process
certain fractions or cuts that contain
naphthenic acids.
TAN number,
Critical Factors 425°F - 750°F; Has been reported
from 350°F - 800°F
Affected CS, low alloys, 300 SS, 400 SS, and Ni

Materials base alloys
Affected Crude and vacuum distillation unit

Equipment transfer lines.
Localized, pitting in high velocity

Morphology
area.
2% - 2.5% molybdenum shows

Prevention improved resistance; Change or
blend crudes; Inhibitors
RT or UT Thickness; Monitor TAN,

Inspection
sulfur, Fe, and Ni contents

Sour Water Corrosion (Acidic)
Corrosion of steel due to acidic sour
water containing H2S at a pH
Description of
between 4.5 and 7.0. Carbon dioxide
Damage
(CO2) may also be present.
H2S content, pH, temperature,

Critical Factors
velocity and oxygen content.
Affected Primarily CS; SS, Cu alloys, and Ni

Materials base alloys usually resistant
Affected Overhead system of FCC, coker gas

Equipment fractionator plants.
General thinning. Localized under

Morphology
deposit
Material selection; 300 SS < 140°F;

Prevention Cu and Ni resistant, but Cu
vulnerable in ammonia
RT or UT Thickness; Monitor pH of
Inspection ovhd accumulators; Corrosion
coupons

Sulfuric Acid Corrosion
Sulfuric acid promotes general and
localized corrosion of carbon steel
Description of
and other alloys. Carbon steel heat
Damage
affected zones may experience
severe corrosion.
Acid concentration, temperature,

Critical Factors alloy content, velocity,
contaminations.
Order of increasing resistance: CS,

Affected
316L, Alloy 20, high Si cast iron, high
Materials
Ni cast iron, Alloy B-2 and Alloy C276
Affected Sulfuric acid alkylation unit, waste

Equipment water treatment.
Morphology General in nature
Materials selection; Proper operation;

Prevention
Caustic wash to neutralize
UT or RT of turbulent zones and

Inspection
hottest areas; Corrosion coupons

DM.V. Environment-Assisted Cracking
1. Polythionic Acid Stress Corrosion Cracking (PASCC)

2. Amine Stress Corrosion Cracking
3. Wet H2S Damage (Blistering/HIC/SOHIC/SSC)
4. Hydrogen Stress Cracking – HF
5. Carbonate Stress Corrosion Cracking (ACSCC)
6. High Temperature Hydrogen Attack (HTHA)
7. Titanium Hydriding

Polythionic Acid Stress Corrosion Cracking (PASCC)
SCC normally occurring during shutdowns,
startups or during operation when air and
moisture are present.
Description
of Damage Cracking is due to sulfur acids forming from sulfide
scale, air and moisture acting on sensitized
austenitic stainless steels.
Environment (scale)
Material in sensitized condition
Critical
Residual Stress.
Factors
Sensitization occurs 750°F - 1500°F
(formation chromium carbide in grains boundary)
Affected Sensitized austenitic SS; 300 SS, Alloy 600/600H,

Materials and Alloy 800/800H
Affected All unit sulfur contain environment

Equipment FCC, hydro processing, crude coker
Morphology Occurs in weld, crack propagates intergranularly.
Material selection; Flush with alkaline or soda ash

to neutralize or purge with nitrogen or
Prevention
nitrogen/ammonia; Keep firebox above dewpoint;
Heat treatment at 1650°F
Inspection Flapper disc sanding to remove deposits and PT

Amine Stress Corrosion Cracking
SCC type in aqueous alkanolamine systems
used to remove/absorb H2S and/or CO2 and
their mixtures from various gas and liquid
hydrocarbon streams.
Description of
Damage
Found at or adjacent to non-PWHT’d carbon
steel weldments or in highly cold worked
parts.
Tensile stress, amine concentration and

Critical Factors
temperature.
Affected
CS and low alloys
Materials
Affected All non PWHT CS pipe/equip. in lean amine

Equipment services (absorber, stripper, regenerator, etc.)
Surface breaking flaws, primarily in

Morphology
weld/HAZ. Parallel to weld.
PWHT all CS welds; Material selection (clad

Prevention or solid); Water wash non-PWHT CS prior to
welding, heat treatment or steam out
Crack detection best with WFMT or ACFM; PT

Inspection
usually not effective; SWUT crack depths; AET

Wet H2S Damage (Blistering/HIC/SOHIC/SSC)
pH, H2S level, contaminant, temperature

Blistering Critical Factors Hardness, microstructure, strength
Damage that result as bulge on the ID/ Tensile stress level.
OD from hydrogen atoms that form
during the sulfide corrosion process on
surface of steel, that diffuse and collect at Affected
Carbon steel and low alloy steel
a discontinuity. Materials
Hydrogen Induced Cracking (HIC): Affected

All equipment where wet H2S is present
Hydrogen permeation into grain Equipment
boundaries/discontinuity assist stress
Description of
cracking
Damage
Coatings or alloy cladding; Water wash to
Stress Oriented (SOHIC) dilute HCN or inject ammonium
A similar cracking mechanism to HIC but Prevention polysulfide's to convert to thiocyanates;
driven by local stresses rather than HIC-resistant steels; PWHT can prevent
hydrogen permeation. SSC and help with SOHIC; Inhibitors
Sulfide Stress Cracking (SCC)

A type of hydrogen cracking under the
influence of wet H2S and tensile stress. Monitor free water phase; Crack detection
Inspection best with WFMT, EC, RT or ACFM; SWUT
for crack sizing; AET

Hydrogen Stress Cracking - HF
Hydrogen Stress Cracking is a form of

Description of environmental cracking as a result of
Damage exposure to aqueous HF acid
environments.
Hardness, strength and stress of metal.

Critical Factors
HF environment exposure
Affected
CS and low alloys
Materials
Affected
All exposed HF environment.
Equipment
Intergranular crack, surface crack on

Morphology
welds.
PWHT; Weld hardness < 200 HB and no

localized zones > 237 HB; CS with Carbon
Prevention
Equivalent < 0.43; B7M Bolts; Coatings or
alloy cladding
Inspection WFMT for cracks; Hardness testing

Carbonate Stress Corrosion Cracking
Surface breaking cracks that occur adjacent
to carbon steel welds under the combined
Description of
action of tensile stress in systems containing
Damage
a free water phase with carbonate, where
some amount of H2S is also present.
Residual stress, water chemistry (carbonate),

Critical Factors
pH alkaline, H2S content, ammonia content.
Affected
CS and low alloys
Materials
Affected Fluid catalytic cracking, fractionator overhead.

Equipment Downstream wet gas compression.
Morphology Crack propagate parallel to weld / HAZ
PWHT at 1150°F; Material selection; Coatings

or alloy cladding; Water wash non-PWHT
Prevention
prior to steamout or heat treatment;
Inhibitors
Monitoring of pH and Carbonate

Inspection concentration; WFMT or ACFM for crack
detection; SWUT for crack depth; AET

High Temperature Hydrogen Attack (HTHA)
Exposure to hydrogen at elevated temperatures and
pressures.
The hydrogen reacts with carbides in steel to form

methane (CH4) which cannot diffuse through the
Description of steel. The loss of carbide causes an overall loss in
Damage strength.
Methane pressure builds up, forming bubbles or

cavities, microfissures and fissures that may combine
to form cracks.
Temperature, hydrogen partial pressure, time and

Critical Factors
stress.
Order of increasing resistance: CS, C- 0.5Mo, Mn-

Affected
0.5Mo, 1Cr, 1.25Cr, 2.25Cr-1Mo, 2.25Cr-1Mo-V, 3Cr,
Materials
5Cr
Affected Hydro processing Unit, hydrotreaters, catalytic

Equipment reformers, hydrogen producing unit
Surface decarburization (metallography)

Morphology Bubbles / cavities (SEM)
Cracking and fissuring intergranular, blister.
Alloys with Cr (> 5 Cr) and Mo or tungsten and
Prevention vanadium; Use a 25°F to 50°F safety factor; 300 SS
overlay and/or roll bond clad material
UT using combination of velocity ratio and
backscatter (AUBT); In-situ metallography; VT for
Inspection blistering; WFMT and RT in advanced stages with
cracking Acknowledgement: API RP 571, 2011

Damage Mechanism in Refinery Area

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Damage Mechanism in Refinery Area

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Damage Mechanism in Refinery

based on API RP 571, 2nd edition 2011

1. Introduction to Damage Mechanism

Mechanical / Metallurgical Degradation

1.Loss of Wall Thickness

1.Environmentally Assisted Cracking

1.Refinery Chemical Acid/Alkaline

Acknowledgement: API RP 571, 2011 & www.matthews-training.co.uk

Description of Prevention / Inspection and

Acknowledgement: API RP 571, 2011

• New Equipment (no • DM affect the • To determine if the

Acknowledgement: API RP 571, 2011 & www.matthews-training.co.uk

Corrosion Non- Corrosion

Stress Chemical (pH)

Mechanical / Metallurgical Not corrosion, failure mode

Damage T > 400F, serious attack

1.Environmentally Assisted Process environment, mostly

1.Refinery Chemical Susceptible in Refinery

Acknowledgement: API RP 571, 2011 & www.matthews-training.co.uk

Affected Hot wall in FCC, catalytic reforming,

Prevention Addition of 0.7% Cr

Inspection Full thickness sample metallography

Acknowledgement: API RP 571, 2011

Carbide phase is unstable and

Hot wall in FCC, catalytic reforming,

Morphology Not visible (unless with metallography)

Prevention Minimize exposure to elevated temps

Field metallography or removal of

Acknowledgement: API RP 571, 2011

Acknowledgement: API RP 571, 2011 & www.matthews-training.co.uk

Carbon and chromium content

Thick wall operates at elevated

Single or multiple cracking with flat

Material design for low

Acknowledgement: API RP 571, 2011

Affected Primarily 2.25Cr; Older 2.25Cr manuf.

hydro processing units,

Pressurization sequence - MPT of

Impact test sample blocks from

Acknowledgement: API RP 571, 2011 & www.matthews-training.co.uk

Loss in toughness due to a

885°F (475°C); 600°F - 1000°F

Affected Alloys containing a ferrite phase; 400

Affected Tower - internal trays at FCC, crude,

Not visible (unless metallography)

Use low ferrite or non-ferritic alloys;

Impact/bend test samples; Cracking

Acknowledgement: API RP 571, 2011 & www.matthews-training.co.uk

1000°F - 1750°F, exposure time,

Affected Ferritic, martensitic, austenitic, and

SS cyclones, piping / valves in high

SS with sigma may have lack of

Testing of samples; Cracking during

Grain size. Single is best. Fine is

Combination of techniques; Tubes

Temp swings exceeding 200°F

hydrogen mix points in

Crack at surface. Transverse and

Design and operation; Liner to

Inspection VT, MT/PT, SWUT for cracking

Acknowledgement: API RP 571, 2011

Local overheating above design

Affected All fired heater tube materials and

Affected Boiler/fired heater tube. Hydro