Corrosion Mechanism
Range (F)
Graphitization
Softening (Spheroidization)
Temper Embrittelment
Strain Aging
(Embrittlement)
Description Temp.
Change in microstructure after long 800-1100 F
term oper of CS & 0.Mo steel
Loss in strength, ductility & creep Severe > 1000 in 5 yr
resistance Slight 850 in 30-40 yr
FeC decompose into graphite nodules
Change in microstructure of steel 850-1400 F
after elevated temp exposure. In CS
carbide agglomerate from plate like to at 1300F - few hours
spheroidal form, in LAS (1-0.5Cr) from at 850F - several years
finely dispersed to large
agglomerated carbide.
Loss in strength (up to 30% usually
accompanied by increase in ductility)
and/ or creep resistance.
Reduction in toughness in certain LAS 650-1070
due to metallurguical change due to (More quickly at 900, but
long term operation. This cause more severe after LT at
upward shift in ductile to brittle 850)
transition temp by CVN
(May result in BF during s/u and s/d)
Combined effect of deformation and Intermediate temp (with
aging at intermediate temp in old deformation)
vintage CS and C-0.5MO steel results
increase in hardness, strenght and
decrease in ductility and toughness
885oF Embrittlement Loss in toughness due to metallurgical 600-1000 F
change in alloys containing FERRITE (thousands of hrs may be
PHASE due to high temp exposure reqd at 600)

Sigma Phase Embrittlement Formation of sigma phase results in 1000-1700 F

loss of fracture toughness in SS due
to high temp exposure

Brittle Fracture Sudden rapid fracture under stress --

(R/A) with little or no ductility or
plastic deformation

Creep & Stress Rupture At high temp metal can slowly deform Threshold temps
under load below yield stress (time
dependent) leading to rupture
Thermal Fatigue TF is the result of cyclic stresses No set limit. As practical
caused by variations in temp resulting rule cracks may occur if
in cracking where DE is constrained temp swing exceeds 200F
(under repeated thermal cycling)

Short Term Overheating Stress Permanent deformation occuring at --

Rupture relatively low stress levels due to
localized overheating results in
bulging & stress rupture

Steam blanketing Normal heat flow results in formation --

of discrete steam bubbles (nucleate
boiling) on tubes ID, when heat flow
disturbs, bubbles join to form steam
blanket known as Departure from
Nucleate Boiling (DNB). Tube rupture
occurs rapidly due to SHORT TERM
OVERHEATING (in few minutes)

DMW Cracking Cracking occurs in ferrtic (CS or LAS) Temp >510F (260C)
side of weld with Aust (300 SS or Ni signifcant thermal
alloy) at high temp resulting from expansion / fatigue stress
creep damage, fatigue cracking, in Ferr to Aust joint
Sulfide stress cracking or H2
disbonding (PWHT will not prevent
cracking)
Thermal Shock A form of thermal fatigue cracking - --
Thermal shock occurs when high and
non-uniform thermal stress develop in
short time due to diff expansion or
contraction, usually when colder
liquid contacts a warmer metal
surface.

Erosion / Erosion-Corrosion Erosion: Accelerated mechanical --

removal of surface material by
relative movement, or impact from
solids, liquids, vapor etc.

Erosion-Corrosion: when corrosion

contributes to erosion to remove
protective film or scale expose metal
to further corrosion

Cavitation Form of EROSION caused by the --

formation and instanteneous collapse
of tiny vapour bubbles, the bubble
may contain vapor phase of liquid, air
or other gas, these collapsing bubbles
exert severe localised impact forces
and result in metal loss

Mechanical Fatigue Machanical degradation that occurs --

when component exposed to cyclic
stresses for an extended period,
resulting in sudden failure. These
stresses arise by mechanical loading
or thermal cycling well below yield
strength.
Vibration Induced Fatigue Form of mechanical fatigue in which --
cracks are produced as result of
dynamic loading from vibration, water
hammer or fluid flow.

Refractory Degradation Both thermal insul and erosion resist --

refractories susceptible to mech
damage (Cracking, spalling & erosion)
and corrosion due to oxidation,
sulfidation, and other high temp
mechanisms

Reheat Cracking Cracking of metal due to stress Above 750 F

relaxation during PWHT or inservice at
elevated temp, mostly in heavy wall
sections.
Gaseous Oxygen Enhanced Many metals are flammable in oxygen
Ignitiion and Combustion & enriched air (>25% O2) at low
pressures which are non fllammable
in air. Spontaneous ignition of metals
and non-metals can cause fires and
explosion in O2 rich gaseous
environments if not properly
designed, operated or maintained.
 4.2. Mechanical and Metallurgical Damages - All Industries
Affected Not Affected Affected Equipment
metallurgy
CS & .5Mo steel Bainitic grades less 1) hot piping and eqpt in
(upto 1% Mo) susceptible FCC, catalytic ref and coker
Si & Al have negligible unit.
effect 2) Few failures directly due
to graphitization.
3) Severe eye brow GT
lowers CRS.
4) Seldom occurs on
boiling surface tubing

CS, LAS i.e. C-0.5Mo, Annealed steels more hot piping and eqpt in FCC,
1-9% Cr-Mo resistant than normalized catalytic ref and coker
Coarse grain more units
resistant than fine grain
Si-killed more resistant
than Al-killed

Primarily 2.25Cr-1Mo C-0.5Mo, 1Cr-0.5Mo and 1) Few failures directlu

(old gen prior to 1.25Cr-0.5Mo not much related to TE.
1972 particular affected 2) Hydroprocessing units
suscepitble) and 3Cr- (Reactors, hot feed / eff
1Mo (lesser extent) exchangers & hot HP
Weld material more seperators, FCC reactors
affected

Old CS (pre 1980) Steels made by BOF and Most likely in thk wall
with LARGE GRAIN fully killed with Al not vessel made from
SIZE and C-.5 Mo susceptible susceptible material not
stress relieved.
400 SS (e.g. 405, 1) Refineries limit ferritic
409, 410, 410S, 430 SS to non press parts .e.g.
& 436), DSS like fractionation trays in FCC,
2205, 2304 and crude, coker units.
2507 2) Cracks when weldings
trays of 409, 410
3) DSS HE tubes > 600F

300 SS wrought, sigmatized wrought 1) SS piping, cylcones,

welds and cast SS materials still stuiable at valves in HT FCC regen
(HK, HP having high operating temp service.
10 -40% ferrite 2) 300 SS overalys, TTS
content) welds during PWHT for Cr-
400 Series (with 17 Mo base metal.
Cr or more ) and 3) SS tubes susceptible
Duplex SS

Older CS & LAS Sec VIII-1 Eqpt subject to ASME Sec 8 Div 1 vessels
prime concern requirement of Ucs 66 before Dec.1987 Add + Thk
(impurities) & 400 300 Series SS wall eqpt during start-up/
series SS also shutdown and Hydrotests
susceptible at amb temp.

All Metals & Alloys -- 1) HT Eqpt operating above

creep range e.g. Heater
tubes, tube supports,
hangers and furnace
internals, FCC reactor, H2
reforming furnace tubes.
2) Low creep ductility
failures found in weld HAZ
at nozzles cat reformer.
3) DSM welds (Fer to Aust)
due to TE stress.
All materials of -- 1) Mix points of hot and
construction cold streams e.g. H2 mix
point in HP units, de-
superheater or
attemporators.
2) TF major problem in
coke drum shells & skirts.
3) In steam gen common
location at attachment bw
SH and RH tubes.
4) Steam soot blowers if
frist steam exit contain
condensate

All FH tubes and -- 1) All boilers & FH tubes

common materials of 2) Furnaces with coking
construction tendency crude, heavy oil
HP and coker units fired
harder to maintain outlet
temp prone to localized
heating.
3) Refractory lined equpt in
FCC (refractory damage)

Carbon steel and -- All steam generating units

Low alloy steel (Fired boilers + WHB, H2
reformers & FCC units),
Failures occur in super
heaters and re-heaters
during s/u when
condensate blocks steam
flow.

CS & LAS welded to -- Overlayed CrMo nozzles to

Aust SS. solid SS pipe welds in HP
Any material comb reactor outlets + H2
having widely reformer 1.25Cr-1Mo
differing thermal exp pigtails to alloy 800
coeff sockolet of tubes + alloy
800 o/l manifold to CS or
1.25CR transfer line +
300SS overlays in PV + all
superheaters and
reheaters have DMW welds
All metals & Alloys -- 1) FCC cokers, catalyic
reforming and HP units in
HT service.
2)Material with lost
ductility such as CrMo
(temper embr) more
susceptible.
3) Equpt subjected to
accelerated cooling to
minimize s/d time

All metals, alloys & -- 1) All types of eqpt

refractories exposed to moving fluid
and/or catalyst are subject
to EC
2) Gas or Liquid born
particles (slurry) in pumps /
compressor
3) HP effluent piping EC by
ammonium bisulfide
depends on vel.
4) Crude and VDU piping
by naphthenic acid

Common materials -- Pump casings, pump

e.g. Copper, brass, impellers (LP side) and
cast iron, CS, LAS, piping d/s orifices and CVs
300, 400 SS & Ni + restricted-flow passages
base alloys. by turbulent flow (eg HX
tubes, venturis, seals)

All engineering alloys -- 1) Thermal cycling: daily

cycles in oper like coke
drums + eqpt in
intermittent service as aux
boiler + quench nozzles
2) Mechanical loading:
pump rotating shafts at
keyways + small dia piping
in vibration + high PD CV
or steam reducing stations
can cause vibration
problem in piping
All engineering -- 1) Socket welds and small
materials bore piping near pumps &
compressors.
2) PSV subject to chatter,
premat pop-off, fretting,
high pd CVs, HE tubes
susceptible to vortex
shedding.

Refractory Matls inccl -- FCC Reactor regenerator

Insulating ceramic vessels, piping, cyclone,
fibers, castable, waste heat boiler, Boiler
refractory brick and firebox and stacks
plastic refractories.

LAS (CR-Mo steels -- Mostly like to occur in

with V), 300 SS & Ni heavy wall vessls in areas
based alloys e.g of high restraint i.e. nozzle
Alloy 800 H welds and heavy wall
piping + HSLA steels are
susceptible
1) CS & LAS are Copper (>50%) and Ni O2 is used in sulfur recvory
flammable in LP O2 (>50%) alloys are fire units (SRU), FCCU, paritial
> 15psig. resistant / non flamm. oxidation units (POX) + O2
2) Aust SS difficult to Alloy 400 highly resistant piping, valves, regulators
below 200 psig. and impingement areas are
3) Al is avoided for vulnerable
flowing O2, if ignited
burns quickly.
4) Easiest to ignite
plastics, rubbers and
HC lubricants.
5) Ti avoided in O2
rich service, can
sustaintain comb at
1psiA O2 press.
amages - All Industries
Critical Factors
Random (nodule) graphitization does not
lower creep resistance.
Chain type reduces load bearing capability
(brittle fracture).
a- Weld HAZ graph occurs at low temp. edge
(Eye brow)
b- Non weld graph occurs along planes of
local yeilding.
Reporting is qualitative (NSMS-None, slight,
moderate, severe)
Rate of SP depends on temp and initial
microstructure
1) Susceptiblity due to elements Mn, Si, P,
Sn, Sb, As
2) Significantly reduces structural integrity
of comp containing crack like flaw
1) Steels made by Bessmer or open hearth
process, rimmed and capped steels with
higher impurities (C & N)
2) Major concern for equipment having
cracks (failure by brittle fracture).
3) Can occur when welding near cracks and
notches in susceptible matl.
Prevention
Adding Cr +.7% to LAS
Mnimize long term exposure
For old material:
1) Limit startup pressure to 25%
of MDP below MPT (safe oper.
envelope).
2) For weld repair, heating to
1150F and rapid cooling to RT
temp reverses TE.
For new material:
1) Best way to Limit J for BM & X
factor WM (100 to 15 for 2.25Cr-
1Mo)
2) Newer less used Equivalent
Phosphorus factor for WM & BM.
1) Not an issue for new steel
with low impuritie and Al >
0.015% to fully deoxidize stl.
2) For old eqpt, pressurize when
temp > MDMT
3) PWHT or buttering of weld
repairs of old equipment
1) Increasing ferrite increases susceptibility
(increase in DBTT).
2) Damage is cumulative due to precip of
embrittling intermetallic phase.
1) Sigma phase occurs in ferritic &
martensitic (Fe-Cr), austenitic (Fe-Cr-Ni) and
DSS in given temp range.
2) Sigma can form in few hours in aust SS if
subject to PWHT (690 C)
3) SS with sigma show complete lack of
fracture toughness by CVN < 500F
4) Precipitation of hard, brittle intermetallic
compund
Important 3 factors for BF:
1) Material Fracture Toughness by CVN,
2) Size, Shape & stress conc. of
flaw
3) Amount of R + A stresses on flaw
Thicker matl have lower resist to BF.
In most cases, BF occurs only below the
charpy impact transition temp.
1) Damage (strain rate) is sensitive to load
and temp. Increase of about 25F or 15% of
stress can cut remaining life in half or more,
depending on alloy.
2) Life become nearly infinite below Thresh
temp
3) Low creep ductility is more severe for
high TS matl and welds + more likely in
coarse grain matl + promoted by some
carbides in CrMo steels.
1) Use of low or non ferrite
alloys SS
2) Embrittlment is reversible by
heat treatment to dissolve
precipitates. Use of PWHT 1100
followed by rapid cooling.
1) Best way to use alloys
resistant to sigma formations
or avoid exp to temp range.
2) 300 SS desigmatized by
solution annealing @1950F for 4
hrs & water quench.
3) Control ferrite to 5-9% for 347
ferrite and 304 still less.
4) For SS clad CrMo, exp time to
PWHT to be limited
1) For new eqpt best to use matl
for low temp (UCS 66 in sec VIII)
2) engineering study with API
579 sec 3 level 1 or 2.
3) Some
reduction in BF by PWHT if not
done and for weld repair +
Warm hydrotest then cold HT to
extend MSOT
1) Little to do except Minimize
metal temp for FH tubes
2) Higher PWHT to minimize
creep cracking of metal with
LCD (1.25Cr-0.5Mo)
3) Creep resitant alloys for
heater tubes for longer life +
Minimuze hot spots on heater
tubes and process side deposits
+ VT and UT thk or strap
measure to assess RL as per API
579-1.
4) For Eqpt, repair of creep
damaged nozzles done by
grinding out affected area,
rewelding and PWHT.
1) Key factor are magnitude of temp swing
and number of cycles
2) Start-up & shutdown increase
susceptibility to thermal fatigue.
3) Damage promoted by rapid changes in
surface temp (thermal shock).
4) Notches (weld toe) and sharp corners act
as initiation sites
1) Usually flame impingement or local
overheating (above design temp)
2) Thk loss due to corrosion reduces Time to minimize hot spot.
failure.
1) Heat flux & fluid flow critical factors
2) Flame impingement from damaged or
misdirected burners
3) on Water side anything that restricts flow
(condensate, tube dent) cause DNB
4) Failure occurs from hoop stress due to
steam pressure at HT
1) cracking occurs due different COE b/w ferr 1) For HT, use NI base filler with
and aust differ by 25-35% (leads to high
stress at HAZ on ferr side)
2) stress on weld higher when Aust filler
used than nickel filler (COE closer to CS)
3) DMW have narrow mixed zone of high
hardness near fusion line with ferr and
susceptible to H2 cracking or SSC.
4) C diffusion from ferr HAZ into weld
reduces creep strenght (at 800 to 950F).
5) In liq ash corrosion environ, ferr will
preferentially corrode.
1) Best prevented by proper
Design & Operation to minimize
Thermal Stresses & Thermal
Cycling. i.e.
-> reduce stress conc, blend
grind weld profile
-> Controlled rate of heating /
cooling during startup / SD
-> DE between DSM material to
be considered.
2) Design should incorporate
flexibility e.g. avoid rigid attach
+ drain on soot blower
1) in FH, burner management
and fouling / deposit control to
2) Use diffuse flame burner
3) in HP unit, install TC in
reactors.
4) Maintain refractory in
serviceable condition.
1) When DNB deveolpes tube
rupture will quickly follow,
proper burner management to
prevernt flame impingement.
2) BFW treatment to prevent
restricted fluid flow
3) VI of tubes for bulging.
COE closer to CS & LAS can
increase life of joint.
2) If 300 SS electrodes used
DMW shuold be located in lower
temp region.
3) Consider buttering on ferr
(6.35mm) & PWHT to minimiz
hardness of mixed zone
4) Install pup piece of
intermediate thermal exp.
1) Temp cycling may initiate fatigue cracks
(SS have higher COE than CS or NI and more
prone)
2) Frature from stress above YS result due to
restraint thermal exp.
3) Thick sections develop high thernal
gradient
1) Prevent flow interruption in
HT line.
2) Minimize severe restraint. 3)
Thermal sleeves to prevent
liquid impingement on PB
4) Review hot/cold injection
points

1) Metal loss depend on vel, conc of 1) improve desing (increase pipe

impacting medium, size & hardness of
particles, CR of matl & Anlge of impact.
Increasing hardness of substrate is common
approach, but not always good indicator of
improved resistance to erosion corrosion
2) For each environment-material
combination there is often threshold
veolocity for metal loss
3) Increased corrosivity by temp, PH reduce
protective film stability and increase
susceptibilyt to E-C
dia to reduce velocity,
streamline bends, wall thk)
2) For Erosion: Hardfacing,
surface hardening, erosion
resistant refractory
3) For EC: Best mitigated by
more CR alloy or altering
process (not by substrate
hardness only)
4) higher Mo for NAC
5) impingment plates and
ferrultes in HX

1) Inadequate NPSH (min head required to 1) Not significatnly improved by

avoid cavitation).
2) Temp approaching boiing pt of liquid
result in bubble formation.
3) Presence of solid or abrasive particles is
not required for cavitaion but accelerate the
damage.
material change. Modify design
or operating change.
2) Best prevented by avoiding
abs pressure to fall below vap
press or change material
properties (changing to more CR
or hihger hardness may not
improve cavit resist).

1) Design: FC initiate at surface notches or 1) Best defense is good design

stress raisers under cyclic loading. Design is that minimize stress conc in
most imp for fatigue resist. cyclic service.
2) Metallurg : For Ti, CS, LAS cracking will 2) Select metal with FL for
not occur below Stress Endurance limit (ratio intended cyclic life.
of EL to UTS is 40%-50%). 3) Mimimize grinding marks,
3) Aust SS & Al dont have EL and FL is nicks, good fit-up and smooth
defined by num of cyles at given stress. transition of welds, mimize weld
4) Finer grain have better fatigue resist than defects, remove burrs or lips by
coarse grain (HT such as quech + tempering machining, use low stress
improves FR). stamps and marking tools.
5) Max cyclical stress ampliude is
determined for 106-107 cylces (desired in
lifetime)
7) Inclusions in metal (dirty steel) have
accelerating effect on FC.
1) high likelihood of cracking when input
load synchronous to natural freq.
2) Lack of stifness or support allows
vibration and cracking initiated at stress
raisers.
1) RLE should be designed for erosion,
thermal shock and expansion.
2) Dry out and curing should be as per
manufacturer specs or ASTM req.
3) Anchors resistant to condensing sulf
acids, HT oxidation and COE near BM.
4) Refractory resistant to erosion and
abrasion and needles compatible with
process env.
1) RC requires high stresses and more likely
in thick sections
2) RC occurs at ET where creep ductility is
insufficient to accomodate strain.
3) Transverse cracks occured in 2.25Cr-1Mo-
V in SAW welds only traced to contaminated
flux (cases in 2008)
4) RC can occur during PWHT or in service at
high temp.
5) Cracks are INTERGRANULAR without
deformation.
6) Stablizing HT and SR of 300 SS for CL-SCC
and PTASCC can cause RC.
1) VIF can be eliminated or
reduced by design and Supports
& Vibrations dampening (matl
upgrade not a solution).
2) Vortex shedding minimized at
o/l of CV and PSV by side branch
sizing and flow stab.
3) Vibration may be shifted
when comp anchored, unless
source removed.
Proper selection of refractory,
anchors and fillers and design &
Installation are the keys to min
ref damage.
1) Joints in heavy wall to be
designed to minimiz restraint
during welding and PWHT.
2) Large grain size less result in
less ductile HAZ making matl
susceptible to RC.
3) Avoid stress conc e.g. long
seam welds mismatch.
4) For 2.25cr-1Mo-V Gleeble
Tensile Screen Test reqd.
5) For 800H, inservice RC risk
reduced using matching weld
metal with AL+Ti<0.7.
6) For 800H operation> 540C
matl requires stabiliz heat
treatment and SR of welds
6) for thickwall SS piping, avoid
PWHT
1) Primary concern in high vel O2 flow
particulate entrainement and impinging on
surface. O2 vel in CS & SS piping should
comply with industry limits (depending on
impigement or non impingement).
2) Ignition temp for most alloys are near
melt point in non flow condition. Actual
system can suffer ignitiion under flow at
room temp and lower due to particle impact.
3) Contamination of O2 system with metal
fines or HC (oil or grease) can cause fire
during startup
4) impingment areas, elbows, valves higher
risk of ignition in flowing O2.
1) O2 fire are sudden event,
best prevention to keep system
clean after insp or maint.
2) Maintain velocity in
recommend limit. Avoid vel >
100 ft/sec 30 m/s).
3) Use only O2 compatible
lubricants.
4) Do not open unnecessary
open O2 systems, for insp to
avoid contamination.
5) Do not use plastic pipe,
minimize person during start up
near O2 system.
6) Thin SS (<1/8") avoided in O2
system.
Inspection / Monitoring Remarks

1) Can only be observed by Competing:

metallography. (Above 1025 --> SPH
2) Evaluation by full thick Below 1025 --> GPH)
sample for metallography
(Replica inadequate
3) Surface or SSF cracks or
microvoid (advanced stage)
difficult to detect

1) Can only be observed thru Competing:

field metallogprahy or sample (Above 1025 --> SPH
removal Below 1025 --> GPH)
2) Reduction in tensile strength
and hardness may incidate
spheroidization.

1) Confirmed thru impact testing NONE

(no effect on upper shelf
energy).
2) Install test blocks of same
heat no and impact test
periodically
3) Ensure pressurization
sequence to avoid BF
4) SEM fractographs show
INTERGRANULAR cracking due
to impurity segragation at GB.

Inspection NOT USED to control When deformation is at

strain aging intermediate temp it is
Dynamic Strain Aging.
Blue brittleness also form
of SA
1) Not thru metallography but NONE
can be confirmed by Impact or
bend test
2) Evaluation by increase in
hardness
3) Impact or bend test of
samples is positive indicator.
4) Most embrittlement cracking
during start up & shutdown <
200F

1) Only confirmed by metall. NONE

2) Cracking appears at welds
during TA & startup below 500F
3) Testing sample removed from
service is most positive
indicator.

1) Cracks are straight, non Temper emb + Strain age

branching devoid of plastic emb + 885F emb + Ti
deformation (cleavage) hydriding + Sigma phase
2) Inspection normally NOT embrittlement
USED to mitigate BF.
3) susceptible vessels should
be inspected for pre-existing
flaws/defects

1) Initial stage (creep voids at Creep damage due to

GB) by SEM metallography very HT + Reheat
2) Bulging of heater tubes cracking
before final fracture.
3) Creep damage micrvoid,
fissures and dim change not
found by one technique but
combination UT, RT, EC dim
measure & replica) used.
4) Remove sample & metallog to
confirm damage.
4) For PV focus on welds of CrMo
alloys in creep range (check by
VT, PT, WFTM, UT)
5) Check FH tubes for diametric
growth, bulges, cracks, bows,
blisters, wall thk measurement
1) Surface cracks, wide and Corrosion fatigue &
often oxide filled due to temp Dissimilar metal cracking
exposure, single or multiple.
2) Cracks propagate
TRANSVERSE to stress and
Dagger shaped and TG.
3) Cracks follow toe of fillet weld
4) Water in soot blower lead to
crazing pattern
5) VT, PT, MT, SWUT (for non
intrusive) and special UT for
heavy wall

1) Localized deformation or Creep/ Stress rupture

bulging (3 to 10% or more)
depend on temp, alloy and
stress level
2) FISH MOUTH Failures by
thinning at fractured surface.
3) In FH, VI, IR montg, TST of
tubes
4) RLE monitor by heat indic
paingt or IR scan
5) Reactor bed and skin TC

1) STHTF always show open Steam blanketing can

bursts with fracture edges cause caustic corrosion
drawn to knife-edge (ductile (Causitic Gouging) +
rupture) Short term Over Heating.
2) Microstructure always show
severe elongation of grain by
plastic deformation at time of
failure.
3) Properly maintain burners to
avoid flame impingement.

1) Cracks form at weld toe in Thermal fatigue &

HAZ of the ferrtic material, Corrosion fatigue &
2) Tubes welds are problem area Creep and SSC.
but support lugs of 300 SS to
400 SS are also affected
3) For new DMW welds, 100% PT
after buttering, 100% UT/ after
PWHT, 100% UT/ RT & PMI.
4) For FH tubes, RT and SWUT
such as top flanges
1) Surface initiating cracks may Thermal fatigue
also appear as CRAZE CRACKS
2) PT and MT to confirm
cracking.
3)Highly localized & difficult to
detect.

1) Localized thk loss in form of Specialized terminology

pits, grooves, gullies, waves, For various Forms e.g.
holes and valleys (directional Cavitation, liquid
pattern). impingement erosion,
2) VT, UT and RT for metal loss fretting etc.,
3) Corrosion coupons and ER
online probes
4) IR scan for refractory loss

1) Looks like sharp-edged pitting Liquid Impingement or

or gouged appearance in low Erosion
pressure zone
2) Cavit pump sound like
pebbles thrased. Accoustic
montg. turbulent areas for
characteristic freq.
3) VT, UT & RT for thk loss.

1) Signature mark is clam Shell Vibration induced

fingerprint that has concentric fatigue.
rings "Beach marks" that results
from Waves" of crack
propagation occuring during
cycles above threshold loading
(single for flaw with stress conc
and multiple w/o stress conc).
2) PT,MT & SWUT to detect
fatigue cracks at known pt.
3) VT of small dia piping to
detect oscillation
4) Vib montg of rot equpt
5) In high cycle fatigue, crack
initiation difficult as crack
initiation is majority of FL.
1) Crack initiate at high stress Mechanical fatigue &
(thread or weld joint). Refractory degradation
2) For Refractory damages, skin
temp measurement
3) Check for visbile & audible
signs of vibration, during start
up, s/d, upset. Measure
vibration.
4) check pipe supports and
spring hangers
5) Damage to insul jacketing
can cause CUI.

3) Excessive cracking, spalling Oxidation, Sulfidation

or lift-off from the substrate, and Flue gas dew point
softening or moisture corrosion.
degradation.
2) In erosive service, refract
may be thinned exposing
anchors.
2) Visual inspection during shut
downs + IR scans

1) RC is INTERGRANULAR and SB Also referred to as Stress

or embedded mostly in COARSE- relief cracking and Stress
GRAINED sections of weld HAZ. relaxation cracking
2) Surface cracks by UT, PT &
MT, EMBEDDED cracks found
only through UT.
3) Inspection for RC in 2.25Cr-
1Mo-V reactor during fabrication
typically done with TOFD or
manual SWUT.
1) external heat damage Not applicable
(glowing pipe or tint) is ind of int
fire due to combustion of
flammable debris
2) Worst situation when
pressure envelope breached. O2
fire can cause metal burning
and struc damage.
3) Sudden ignitiion of metals, it
is difficult to inspect in advance.
4) Black light can be used to
check HC contamination.
4) Signs of ext heat damage or
valve malfunction indicative of
problems.
Corrosion Description
Mechanism
Galvanic Corrosion Corrosion occurs at junction of dissimilar
metals joined together in a suitable electrolyte
or soil containing moisture

Atmospheric Corrosion that occrs from moisture associated

corrosion with atmos conditions. Marine and moist
polluted industrial environ are most severe.
Dry rural environments cause very little
corrosion.

CUI Corrosion of piping, presssure vessel and

structural components due to water trapped
under insulation or fireproofing
Cooling water General or localized corrosion of metals
corrosion caused by dissolved salts, gases, organic
compounds or microbiological activity.

Boiler water General cprrosion and pitting in boiler system

condensate and condensate return piping
Corrosion

CO2 Corrosion CO2 dissolves in water to form carbonic acid

which lowers pH & sufficient qty may promote
general and/or pitting corrosion of carbon steel
Flue Gas Due Point Sulfur and Chlorine in fuel will form SO2, SO3
Corrosion and HCL in combustion and at low temp these
gases condense with water vapor to form
sulfurous, sulfuric and hydrocholric acid to
cause severe corrosion

Microbiologically Corrosion caused by living organism such as

Induced Corrosion bacteria, algae or fungi often with presence of
(MIC) tubercles or slimy organic substances

Soil Corrosion Deterioration of metals exposed to soils

Caustic Corrosion Localized corrosion due to concentration of
caustic or alkaline salts that usually occur
under evaporative or heat transfer conditions.
General corrosion can occur depending on
alkali or caustic solution strength

Dealloying Selective corrosion where one or more

constituents of alloy are preferentially
attacked leaving lower density (dealloyed)
porous structure. Component failure may
occur due to degradation of mechanical
properties.

Graphitic Corrosion Cast iron comprises of graphite particles in

iron matrix. GC if form of dealloying in which
iron matrix is corroded, leaving corrosion
product and graphite (with loss of strength,
ductility and density). It usually occurs under
low pH, especially in contact with soil or water
high in sulfate.
 4.3.Uniform or Localized Loss of Thic
Temp. Range (F) Affected metallurgy Not Affected

-- All metals except most noble Most noble

metals metals

CR increase with temp Carbon steel, LAS and Cu SS

upto 250 F. Above 250F alloyed Al
surfaces usually too dry
for corrosion, except under
insulation

Insulated piping / eqpt in Carbon steel, LAS, SS and

intermittent service or Duplex SS
operating at:
CS & LAS: 10 to 350 F
SS & DSS: 140 to 400 F

For insulated comp

corrosion becomes severe
at metal temp b/w 212F to
350 F (insulation stays
wet)
Scaling potential for Fresh CS, all grades of SS, copper,
water, if process side aluminum, titanium and Ni
temp >140F (60C) base alloys.

Brackish or salt water

temp > 115F (46C) may
cause serious scaling.

Primarily CS, some LAS,

some 300 Series SS and Cu
based alloys

Increasing temp incr CR Carbon steel and low alloy 300 SS are
upto point where CO2 is steels highly resistant
vaporized 400 SS and DSS
also resitant
H2SO4c acid DP 280F Carbon steel, Low alloy steels
HCL acid DP 130F and 300 SS

organisms can survice Most common materials of

temps from 0 to 235 F construction incl carbon and
low alloy steel, 300 SS, 400
SS, Aluminum, Copper & Ni
base alloys

Corrosion rate increase Carbon steel, Cast iron &

with increasing metal ductile iron
temp
1) Exposure to high Primarily carbon steel, low Alloy 400 and
strenght caustic can cause alloy steels and 300 Series some Ni base
General corrosion of CS at SS. alloys exhibit
temp > 175 F and very much lower CR
high CR above 200F.

Primarily copper alloys (brass,

bronze, tin), Alloy 400 and
cast iron

Primarily gray cast iron, but White iron not

also nodular and malleable subject to this
cast iron (last two crumble damage as
when attacked) there is no free
graphite
form or Localized Loss of Thickness - All Industries
Affected Equipment
HX susceptible if tubes matl
different from TS or baffles and
if salt water cooling used +
Buried pipelines + ship hulls
are typical locations
1) Piping & eqpt with oper
temp low to allow moisture to
be present.
2) Coating poor condition
2) Eqpt cycled b/w ambient
and high / low oper temp.
3) Eqpt shutdown for long
period (unless mothballed)
4) Pipe resting on support may
trap moisture.
5) Bimetallic connections such
as Cu to Al
1) Eqpt with damaged insul,
vap barrier, weatherproof or
mastic or protrusion thru
insulation.
2) Eqpt with welded insul
support rings, at ladder &
platform clips, lifting lugs,
nozzles.
3) Damaged or leak steam
tracing
4) Local paint damage
4) Dead legs, valves and
fittings
5) missing caulking & insul
plugs should be replaced and
sealed.
Critical Factors
1) For GC, 3 cond must be met, Presence
of electrolyte, different alloys (A+C) &
electrical connection
2) CR high if small A to C ratio.
3) More noble material to be coated
4) Same alloy may act as anode &
cathode to surface films, scale or local
environ.
1) Critical factors include location
(industrial, marine, rural); moisture
(humidity); temp; presence of salts,
sulfur compounds and dirt.
2) Marine environ very corrosive (20
mpy) & indust environ with suflur
compounds can form acid (5-10 mpy)
3) Inland moderate CR (1-3 mpy)
4) Dry rural environ low CR (<1mpy)
5) Cl, fly ash, H2S from cooling tower,
furnace stacks acceler corr.
1) Poor design or installation allow water
to trap can increase CUI
2) Cyclic or intermittent service can
increase CUI
3) Eqpt operating below DP, Cl leach
from insulation, plant located in area of
high rainfall or marine are prone to CUI
4) Environment that provide airborn
contaminants like Cl, SO2 increase CUI
CW corrosion is concern with
water-cooled HX and cooling
towers across all industries.
External treatment system +
deaerating equpment +
feedwater lines, pumps, and
economizers + steam
generation system on both the
water and fire sides +
condensate return system.
1) BFW and condensate sys.
2) Effluent gas of shift
convertors in H2 plant when
temp drop below dew point
300F (CR=1000 mpy noted).
3) OH sys of regenertors on
CO2 removal plant
1) CW corrosion and fouling closely
related.
2) increasing CW o/l temp increase
fouling and corrosin rate.
3) increasing O2 increases CS corr.
4) Low velocity (<3 FPS) likely to cause
fouling. Accelerated corrsion by CW if
used on shell side
5) Cu/Zinc alloys can suffer SCC if
ammonia or ammonium compound
present in CW
6) ERW pipe can suffer weld / HAZ
corrosion in fresh or brackish water.
7) Ti may suffer hydrding embrittle
ment, generally above 180F when
connected to anodic material.
1) BFW corrosion is usually result of
dissolved gases, O2 and CO2 causing O2
pitting corrosion and carbonic acid
corrosion
2) Corrosion protection in boiler by
continuous maintaining magnetite
(Fe3O4) layer
3) Ammonia SCC can occur due to
hydrazine, neautralizing amines or
ammonia comp of Cu-Zn alloys
1) increasing partial press of CO2 causes
lower pH and higher CR.
2) Corrosion occurs in liq phase and
where CO2 condenses from vapor.
3) Increasing Cr in steels offers no
improvement in resist unitl min of 12%
reached.
1) Fired heaters and boilers
burning fuel with S have
potential for H2SO4 DPC in
economizer and stack.
2) HRSG with 300 SS heaters
can suffer CL-SCC from gas
side if temp water < HCL DP +
if comb turbine atmosph
include Cl (from cooling tower
drift)
1) Most often found in HX,
bottom of storage tanks, piping
with low flow and in contact
with soil.
2) Also found in Eqpt when
hydrotest water not removed.
3) Storage tanks and water
cooled HX if CW treatment not
proper.
4) Fire water systems can be
affected.
Underground piping and eqpt,
buried tanks, bottoms of
storage tanks and structures
1) Since all fuel contain S, sulfurous and
sulfuric acid DP corrosion can occur if
metal temp is below DP.
2) Dewpoint of sulfuric acid depend on
conc sulfur trioxide in flue gas, but
typically 280F (138C).
3) Dewpoint of HCL acid depend on conc
of hydrogen chloride, but typically 130F
(54C).
1) stagnant or low flow conditions of
water promote m-organism growth.
2) Organisms can survive under severe
cond e.g. lack of O2, light or dark, high
salinity, pH 0 to 12
3) System become inoculated unless
controlled
4) All organism require source of C, N &
P for growth and thrive on inorganic
substances (S, NH3, H2S) and organics
(HC, organic acids).
5) Leakage of H2S or HC may lead to
massive biofouling and corrosion
1) No single parameter, multiple
characteristics must be combined to
estimate soil corrosion as in ASTM STP
741, API RP 580, 581.
2) Soil resistivity used to estimate
corrosivity. Soil with high moisture, high
dissolved salt conc, low pH are most
corrosive.
3) S-A interface more susceptible bec of
moisture & O2 availability
4) Galvanic corrosion, dissimilar soil,
stray current, MIC factors affect SC.
1) Most often in boilers, steam
generators, HX
2) Accel localized corrosin may
occur in preheat HX, furnace
tubes, transfer line in crude
unit.
1) underground CI pipe
exposed to certain soils.
2) in CW, HX tubes (Brass, Al
brass) in some brackish and
sea water.
3) BFW piping and aftter boiler
comp incl bronze pumps,
monel strainers, brass PG.
Graphitic corrosion can occur in 1) GC is usually limited to very specific
soft water, salt water, mine
water, dilute acid and in u/g
piping e.g. FW piping, pumps, phase below 200F (93C).
impeller, fire water piping.
1) caustic sometimes added for
neautralization or as reactant (may enter
BFW while regen of demins)
2) Some process units use caustic soln to
remove sulfur comp, or chloride comp.
3) A conc mechanism must exist to build
caustic strength (DNB, evap and
deposition)
1) Dealloying occurs usually with very
specific alloy-environ comb.
2) Extent of dezincification increase with
increasing zinc content.
m-structure-environ combination.
2) Damage occurs with moisture or aq
3) Graphite is cathodic to Iron matrix,
preferentially corrodes and protects
graphite in water or soils.
4) Most damage in stagnant cond with
high sulfate.
Prevention
1) Best method is good design.
Different alloys should not be in
contact in conduct environ.
2) Coating helpful but more noble
materal to be coated
3) For piping, insulating bolt
sleeves & gaskets may be used
4) in GI pipe, large A to small C
protects steel (below 150F)
Surface preparation and proper
coating application are critical for
long-term protection
1) Since majority of matl prone, so
best is to use paint/coating,
maintain insulation / sealing.
2) Flame spray Al coating on CS,
corrodes preferentially by galvanic
action to protect CS.
3) High quality non metallic
coatings provide long term
protection.
4) Low Cl insul should be used on
300 SS.
5) AL foil wrapped on SS piping and
eqpt is effective barrier under
insulation.
6) Closed cell foam glass insul
holds less water than mineral wool.
Inspection / Monitoring
1) Active material suffer general thk loss or
crevice, groove or pitting corrosion
2) Anode corrosion higher near junction
3) Visual inspection & UT gauging are effective
to detect galvanic corrosion.
1)Attack can be general or localized, if
moisture trapped
2) If no coating, thk loss can be general by
iron oxide (red rust) scale forms.
3) VT and UT for thk loss
1) CS & LAS : Subject to localized pitting
corrosion or thk loss. After insul removal CUI
appears as loose, flaky scale
2) 300 SS & DSS : localized pitting. For 300 SS
calcium silicate insul can cause Cl-SCC
3) Inspection plan for CUI should be
systematic approach, consider oper temp,
type and age / cond of coating and insul, sign
of insul, sealant damage.
4) If external covering in good condition, no
reason to suspect damage behind.
5) Use multiple techniques to develop cost
effective approach i.e. e.g. partial / full insul
removal, UT thk, Profile RT (small bore piping),
Neutron BS for wet insul, deep EC insp, IR scan
for wet insul, guided wave UT
1) Design for process side inlet
temp < 140F (60C)
2) Min and max velocity must be
maintained in salt water system
3) Upgrade tube metallurgy in high
Cl, high process temp, low vel
systems
4) Periodic cleaning of tube ID and
OD for clean HT surfaces
5) CW should be on U-tube side to
minimize stagnant areas.
1) O2 scavenging treatment include 1) Corr from O2 is pitting type (redish ferrous
(cat sodium sulfite or hydrazine) in oxide) with very small quantity.
deaerator.
2) If scale /deposit control
/magnetite maintenance treatment type).
scheme does not minimize CO2 in 3) Water analysis commom montg tool to
cond return system, an amine
inhibitor may be required.
1) corrosion inhibitors can reduce
corr in cond system. Vap phase
inhibitors reqd to protect against
condensing vapor.
2) increasing pH > 6 can reduce
corrosion in condesate sys.
3) Upgrading to SS for plant
producing or removing CO2.
4) 400 SS and DSS also resistatn
4) condensate sys experiencing
CO2 corrosion usually due to
operating problems
1) CW corrosion can be general corrosion,
pitting corrosin, MIC, Fouling, SCC.
2) Unfirom corrosion of CS when dissolved O2
present.
3) Localized corrosion may result from
underdeposit corrosion, crevice corrosion or
MIC.
4) Corrosion of ERW weld appears as grooving
along fusion line.
3) Monitor variables that affect corrosion and
founling i.e. pH, O2, COC, bio acitvity, CW o/l
temps, process leaks
4) HX U-factors (performance measure)
provide info on scaling and fouling.
5) EC or IRIS inspection of tubes.
6) Splitting representative tubes.
2) Corr in cond return syst from CO2 tends to
be a smooth grooving of pipe (jagged fir tree
assure treatment system performance.
Parameter incl pH, conductivity, chlorine or
residual biocide, and TDS to check for leaks in
form of organic compounds.
4) NO proactive insp methods
5) Deaerator cracking check by WFMPI
1) Localized thinning or pitting corrosion of CS.
Deep pitting and grooving in area of
turbulence / impingement. (MESA type
pattern)
2) VT, UT and RT for general & local thk loss in
water wetting anticipated.
3) Preferential weld corrosion require angle
probe UT or RT
4)Monitor water analysis (pH, Fe etc)
1) Maintain back end of boiler and
fired heater above sulfuric acid DP
temp
2) For HRSG avoid 300SS in FW
heater if CL in environment
3) in oil fired boilers water wash of
ash, sodium carbonate to be added
to neutralize acid ash.
1) System that contain water
should be treated with biocide such
as Cl, Br, O3, UV light etc. (contd
treatment reqd)
2) Minimize low flow or stagnant
zone
3) Empty hydrotest water, blow dry
to prevent moisture
4) Wrapping and CP of u/g struct
effective to prevent MIC.
5) removal of deposits (pigging,
blasting, chemical clean) and
biocide treatment
1) SC of CS minimized by use of
special backfill, coating and CP (last localized pitting.
two most effective protection)
1) SA corrosion of CS & LAS will cause general
wastage and shallow pits based on how
sulfuric acid condenses.
2) For 300 SS feedwater heater HRSG, Cl-SCC
will have surface breaking cracks.
3) UT thickness of economizer tubes
4) SCC of 300 SS can be found by VT & PT.
1) MIC usually observed as local pitting under
tubercles or deposit.
2) Cup shaped pits within pits in CS or
subsurface cavities in SS.
3) in CW system, treatment effectiveness
measured by bocide residual, microbe count
and visual appearance.
4) increase in loss of HX duty may indicate
fouling from MIC.
5) Foul smelling water sign of trouble.
1) SC appears as external thinning with
2) Poor coating is tell tale sign of SC.
3) Most common method for monitog is to
measure PSP using ref electrode near
structutre (corrected for IR drop)
4) CP should be performed as per NACE RP
0169.
3) Piping may be inspected by inline insp by
inline inspection devices, guided UT, pressure
testing (indirect) or visually.
1) Best prevented thru design.
2) Reduce amount of free caustic
ensuring water flow, burner
management ot minimze hot spot
on boiler tube, minimize alkaline
salt ingress in condensers
3) Caustic injection designed to
allow proper dilution / mixing.
4) CS and 300 SS have serious
corrosion problem > 150F
1) Typically local metal loss as grooves in
boiler tube or LTA under insul deposits.
2) Localized gouging along waterline,
circumferential groove in vertical tube.
3) UT thk useful for general corrosion but
difficult to locate localized loss.
4) UT scan and RT may be used.
3) Injection pt inspected as per API 570.
4) Steam gen eqpt may require VT wih
boroscope.

1) Often difficult ot predict cond for
dealloy in particular environment.
2) Addition of certain alloy
elements can improve resist e.g.
Tin inhibits dealloy of Cu alloys,
admiralty brass inhibited by small
amt of P, As, Sb and
dealumnification of Al-Bronze
prevented by heat treatment to
produce and m-structure.
3) Depending on alloy-environ
comb, CP or barrier coating may be
effective.
1) Ofter there is color change or deep etched
(corroded), but some show no dimensional or
visible change.
2) Attack may be uniform (layer type) or
localized (plug type).
3)Brass dealloy evident by reddish Cu color,
instead of yellow brass color.
4) Graphitic corr turns CI charcoal gray, matl
can be cut with knife.
5) Metallography required to confirm DE.
6) Sign hardness red may accompany DE.
7) Accoustic technique (loss of metallic ring)
and UT attenuation applicable, but not UT
thickness measurement.
8) FFS of dealloyed comp should consider part
brittle with no mech strength

1) Difficult to predict if cond will 1) Damage may be widespread or localized.

cause dealloying in particular 2) damage may not visually noted even if full
environ or service. thickness degraded.
2) Internal graphitic corrosion can 3) Damage area easily gouged with knife.
be prevented by coating or cement 4) Metallograpy reqd to confirm damage.
lining. 5) UT is not good for detecting damage.
3) External graphitic corrosion can 6) Accoustic technique (loss of metallic ring)
be prevented by external coating or and UT attenuation applicable.
CP in severely corrosive coil. 7) Significatn red in hardness of dealloy.
Related Mechanism

Soil corrosion

Corrosion under
insulation (CUI)

Atmospheric
corrosion +
Oxidation +
Chloride SCC
MIC + Cl-SCC +
galvanic
corrosion

CO2 corrosion,
corrosion fatigue
and
erosion/erosion-
corrosion

Boiler water
corrosion +
carbonate cracking
At lower temp HCL
acid may condense
and promote HCL
corrosion of CS and
Cl-SCC of 300 SS

Cooling water
corrosion

Galvanic Corrosion
Also referred as
Caustic gouging or
ductile gouging.
Related mech is
Steam blanketing
(DNB)

Dealloying often
referred to by
element removed
as dezincification,
destannification,
denicklification and
graphitic corrosion.
Also referred to as
Selective Leaching.

Also known as
Selective leaching,
GC is form of
dealloying of cast
iron. Do not
confuse with
Graphitization.
Corrosion Description
Mechanism
Oxidation O2 reacts with CS and other alloys at high
temperature converting metal to oxide scale.
Oxygen is present in air (20%) used for
combustion in fired heaters & boilers.

Sulfidation Corrosion of carbon steel & other alloys from

reaction with sulfur compounds in high temp
environment. Presence of H2 accelerates
(sulfidic) corrosion

Caruburization Carbon is absorbed into material at elevated

temp while in contact with carbonaceuos
material or environment.
Decarburization Condition where steel loses strength due to
removal of carbon and carbides leaving iron
matrix. Decarburization occurs during
exposure to high temps, during Heat
Treatment, exposure to fires or HT gases.

Metal Dusting MD is form of carburization resulting in

accelerated localized pitting in carburiz gases
and/or process stream containing C and H2. Pit
form on surface and may contain soot or
graphite dust.
Fuel ash corrosion Accelerated high temp wastage of matls
occurs when contaminats in the fuel (S, Na, K
and/or V) form deposits and melt on metal
surfaces of fired heaters, boilers & Gas
turbines. Molten salts (slag) dissolve surface
oxide and enhance transport of O2 to surface
to reform iron oxide at expense of tube wall or
comp. Actual cause of wastage is corrosion of
clean unproteted steel

Nitriding A hard, brittle surafce layer will develop on

some alloys due to exposure to HT process
containing high levels of N2 compounds such
as ammonia or cyanides, particularly under
reducing conditions.
 4.4. High Temperature Corrosion (>
Temp. Range (F) Affected metallurgy Not Affected

CS oxidation becomes All carbon steel and low alloy

signif > 1000F (538C) steel.
All 300 & 400 SS & NI alloys
300 SS resist scaling up to also oxidize depending on
1500 F (816C) comp & temp

Sulfidation of Fe base All carbon steel, low alloy

alloys usually begins steel, 300 & 400 SS.
above 500 F Ni alloys also affected
depends on Cr %
Cu alloys form sulfide at lower
temp than CS

Typically above 1100F to Carbon steel, low alloy steel,

allow C diffusion in to 300 SS and 400 SS, Cast SS,
metal Ni base alloys with significant
Fe content (alloy 600 & 800),
HK/HP alloys
 Carbon steel and low alloy
steels

Usually occurs in temp Low alloy steel, 300 SS, Ni

range of 900 to 1500F alloys, Heat resistant alloys
(Currently no known metal
Damge increases with which is immune to MD at
increasing temp. all conditions)
Corrosion occurs by this All conventional alloys used alloys of 50Cr-
mechanimsn only if metal for process heaters and 50Ni show
temp is above temp of liq boilers susceptible. improved
species resistance

Nitrid begins > 600F Carbon steel, low alloy steel, Ni base alloys
Nitrid severe > 900F 300 SS & 400 SS (containg 30 to
80% Ni) are
(>750F, preferential grain more resistant
boundary nitrid may lead
to micro-crack and
embrittlement)
High Temperature Corrosion (>400F) - All Industries
Affected Equipment Critical Factors

Fired heaters, boilers, 1) In general resist determined by Cr

combustion eqpt, piping
operating > 1000F
content. Increasing Cr level produce
protective oxide scale
2) Presence of water vapor can
signifcant accelerate oxidn rate of some
steel incl 9Cr-1Mo

1) Piping and equpt at high 1) Susceptibility of alloy is by ability to

temp in sulfur containing
stream.
2) Common area of concern
incl FCC + coker + vacuum +
HP units
3) Heaters fired with oil, coke
gas (fuel) with S
4) Boilers & high temp eqpt
with Sulfur containing gas
form protective sulfide scale.
2) Resistance determined by Cr.
Increasing Cr increase resistance to
sulfidation (Ni alloys similar to SS with
similar Cr content).
3) Sulfid primary due to H2S and other
sulfur comp which react to form H2S (CR
not based on S alone).
4) Sulfide scale offers protection depend
on alloy & process severtiy

1) FH tubes most common type 1) Three conditions must exist

of eqpt susceptible to (Carburizing environ + HT > 1100F +
carburization. susceptible material )
2) Coke deposit promote 2) Cond favoring carburization incl high
carburiz, particularly during gas phase C activity (HC, coke, gas rich
decoke cycles where temp in CO, CO2, CH4) and low oxygen
exceeds normal oper temp. potential (min O2 or steam).
3) Carburiz found in Coker 3) In CS & LAS, C react for form hard,
units & catalytic reformers + brittle surface that may crack or spall on
ethylene pyrolosys and steam cooling.
reformers. Carburiz occurs 4) Carburization can cause loss of HT
during decoking cycles. creep ductility, loss of ambent temp
properties (toughness / ductility), loss of
weldabiliy and CR.
5) 300 SS are more resistant than CS
and LAS due to higher Cr & Ni.
1) Any eqpt exposed to high
temp, heat treated or exposed
to fire.
2) Piping & eqpt in hot H2
service in HP units, catalytic
reformer, fired heater tubes +
PV components hot formed
during fabrication can be
affected.
1) Primary FH tubes,
thermowels andfurnace
components in carburizing
environemnt
2) Catalytic reformer heater
tubes, coker unts, GT's,
Methanol reformer outlet
piping , hydrodealkylation
furnaces and reactors
1) Matl must expose to gas with low
carbon activity so carbon will diffuse to
surface & react with gas.
2) Depth of decarb depends on temp
and exp time. Shallow decarb can
slightly decrease strength but no effect
on overall performance (HTHA may be
present).
3) Loss in room temp TS and creep
strength.
1) MD is preceded by carburization and
rapid metal wastage.
2) MD involves complex reactions with
reducing gas e.g. H2, CO, C3.
3) Mechanim of MD:
a- Saturation of metal by carburiz.
b-Precipitation of metal carbides at GB
and metal surface.
c-Deposit of graphite from atmosph on
to metal carbide at surface
d- Decomp of metal carbide under
graphite + metal particles
e- Further deposit of graphite catalyzed
by metal particles
4) MD can occur alternating reducing
and oxidizing conditions
5) In high Ni alloy, MD occurs w/o
formation of metal carbide.
1) Any fired heater, gas
turbines burning fuel oils with
V and Na.
2) FH tubes some times not
affected due to skin temp less
than threshold temp of slag,
but hangers /supports are
affected.
3) Oil fired boilers on fuel w/o V
less prone to Liquid ash
corrosion.
4) For waterwall, if temp below
MP of pysrosulfate (700F),
damage minimized.
5) Steam generating press
<1800 psi nearly immune
Nitrid has been observed in
steam methane reformers,
steam gas cracking (olefin
plants) and NH3 synthesis
plants.
1) Severity of damage depends on conc
of contaminants in fuel, sulfur content
and metal temp.
2) liquid species (slag) are different for
oil and coal ash.
a-For oil ash, superheater and reheater
corr by mix of vanadium pentoxide and
sodium oxide or sodium sulfate (MP ~
1000F). For coal ash, sodium &
potassium iron trisulfate (MP ~1030 t0
1130F).
b- For water wall corr in coal fired, liq
species of pyrsosulfate of Na & K.
c- Reducing cond e.g. flue gas rich in
H2S, CO and H2 aggravate corr (2-5
times faster) bec protective iron oxides
do not form readily (results in proous
iron sulfide whcih is less protective)
1) Temp must be high engough for
thermal breakdown of N from ammonia
or other comp.
2) High gas phase N activity (high pp of
N2) promotes nitriding.
3) Nitriding causes loss of HT creep
strength, ambient mech properties
(toughness / ductility), weldability and
corrosion resistance
Prevention
1) Resistance best by upgrading to
more resist alloy.
2) Cr is primary alloy element to
resist oxidation.
3) Also Si and Al but adverse
effects on mech properties (used in
special alloys for burner tips,
heater supports)
1) Resist generally achieved by
upgrading to higher Cr alloy
2) Eqpt constructed with clad or
solid 300 + 400 SS.
3) Al diffusion treatment of LAS
sometimes reduce sulfidation rates
and scaling
1) Select alloys with strong oxide
layer or sulfide film formers (silicon
& Aluminum)
2) Reduce carbon activity of
environment thru lower temp and
high O2/Sulfur partial pressures.
3) Sulfur inhibits carburization and
often added in small amounts into
process streams of steam/ gas
crackers of olefin & thermal
hydroalkylation units
Inspection / Monitoring
1) CS, LAS suffer thinning and covered with
oxide scale on outer surface.
2) 300 SS & NI alloy have very thin dark scale
(generally no metal loss)
3) Monitor process cond for HT trend
4) Monitor temp with IR scan or skin TC
5) Measure thk loss with external UT
1) Corrosion is most often in form of Uniform
thinning but can also be localized or high vel
erosion corrosion.
2) Sulfide scale covers component
3) Process cond monitg for increae in Temp &
sulfur levels
4) Temp montg by skin TC or IR scan
5) External UT & Profile RT for thinning
6) PMI for alloy verifcation and mixup check
1) Depth of carburization confirmation by
metallography
2) Carburiz can be confirm by substantial
increase in hardness and loss of ductility
3) Volumteric increase in advance stage
4) Incr in Ferromagnetism of some alloys.
5) Formation of metal carbides depleting
matrix of carbide forming element
5) Intial stage inspection is difficult (hardness
and FMR from process side) + Destruictive and
magnetic based tech (ECT) have been used.
6) Determine increase of ferromagnetism
(magnetic permeability) useful for alloys
paramagnetic initialy (austenitic)
7) Advances stages cracking by RT,UT &
magnetic technique
1) Control the chemistry of gas
phase and alloy selection (AP RP
941).
2) LAS with Cr & Mo form stable
carbide & more resistant.
3) Steels for HT H2 should be
selected in a/c with API RP 941.
1) Sulfer (usually as H2S) forms
protective sulfide layer to minimize
carburization & MD (retards Carbon
trasnfer from atmosph to metal &
suppress & graphite nucleation &
growth).
2) Sulfur is catalyst poison in some
units, so H2S in process not always
practical.
2) Al diffusion treatment to
basemetal is sometimes beneficial.
1) Damage verified by metallography.
2) Damage occurs on surface exposed to gas
but thru wall in severe case.
2) Decarb layer free of carbide, CS is pure iron.
3)Field metallography & replica (FMR) can
confirm decarb.
4) Decarb results in softern confirmed by
Hardness testing
1) In LAS wastage can be uniform but usually
in small pits filled with residue of metal oxides
and carbides.
2) Corrosion product is volumnous carbon dust
contains metal particles, metal oxides and
carbides. Flow can sweep dust leaving behind
pitted metal.
3) In SS &HAS local attack with deep and
round pits.
3) Metallography shows metal is heavy
carburized under attack surface.
4) For heater tubes compression wave UT
efficient method & scans large areas.
5) RT for pitting and wall thinning
6) VI on internal surface
7) Filtering of cooled furnace or reactor
effluent may yeild metal particles tell tale sign
of MD.
1) FAC can be prevented by 1) For CAC of SH & RH tubes, ash deposit in
blending or changing fuel sources two layers. Hard scale when removed steel
(min contaminants) & maintain hot surface has "alligator hide" appearance due to
component below temp of MP of shallow grooves.
deposits. 2) For water wall tubes burning oil,
2) Burner design + management appearance is series of circumf grooves ro
reduce flame impingement and hot cracks (actually v shaped corrsosion fatigue
spots. cracks).
3) Inject special additives into fuel 3) cracks form due to thermal / corr fatigue as
to incr MP of slag or firing with low ash layers builds, falls exp and insul steel to
oxygen. temp spike by 100 F.
4) Change tube hanger & supprt to 4) For coal ash, appearance is smooth
50Cr 50Ni (but design for low stress interface b/w glassy slag and metal.
rupture strength) 5) Visual inspection sufficient to detect hot ash
corrosion.
6) Metal loss severe (100-1000 mpy) with
presence of slag.
6) Tubes need grit blasting to remove
tenacious glass like ash deposit for UT
thickness.

1) Changin to more resistant alloy
30-80% nickel usually reqd.
2) It is usually not practical to
modify process to reduce N2 partial
pressure or lower temp.
1) Nitrid confined to surface, has dull, dark
gray appearance. At initial stage, damage only
seen with metallography.
2) In advanced stage, matl exhibit very high
surface hardness, concern for crack
development in nitride layer.
3)Nitrid of LAS upto 12%Cr cause increase in
volume. Nitride layer can crack / flake.
4) SS from thin brittle layer that may crack or
spall from stress.
5) N diffuses in surface and forms needle like
particles of iron nitride (Fe3N, Fe4N) only
confirmed by metallography.
5) Change in surface color to Dull gray.
6) Hardness testing (400-500HB) can indicate
nitriding.
7) Nitrided layer magnetic, so check 300 SS
for magnetism as screening.
8) ECT in some cases + in advance stage of
cracking PT, UT & RT for cracking.
Related Mechanism

Oxid damage by
Surface scaling (int
oxid not in scope)

Sulfidation also
known as Sulfidic
Corrosion.
High temperature
sulfidation (in H2
Presence)

Severe form of
carburization known
as Metal Dusting
High temperature
hydrogen attack
(HTHA)

MD is also known as
Catastrophic
carburization
Hot corrosion, hot ash
corrosion, molten salt
corrosion, oil ash
corrosion and coal
ash corrosion all
terms used for this
mechanism.
Circumf cracking in
waterwall tubes is
similar to thermal
fatigue aggravated by
a corrosive
environment

Simlar gas-metal
reactions are
Carburization & Metal
dusting
Corrosion Description
Mechanism
Chloride SCC Surface initiated cracks of 300 series SS and
some Ni base alloys under combined action of
tensile stress, temp & aqueous Cl environment
(presence of dissolved O2 increases cracking
propensity)

Corrosion fatigue Cracks develop under the combined effects of

cyclic loading and corrosion, often initiates at
a stress concentration such as a pit in surface.
Caustic SCC SCC characterized by surface initiated cracks
(Caustic in piping & eqpt exposed to caustic (NaOH &
Embrittlement) KOH), adjacent to non PWHT welds

Ammonia SCC Aqueous streams containing ammonia may

cause SCC in some Cu alloys. CS is
susceptible to SCC in anhydrous NH3.

Liquid Metal Cracking that result when certain molten

Embrittlement metals come in contact with specific alloys.
(LME) Cracking is sudden and brittle in nature.
Hydorgen Loss in ductility of high strength steels due to
Embrittlement the penetration of atomic H2 can lead to
brittle cracking

Ehtanol SCC Surface initiated cracks of CS under comb

action of tensile stress and fuel grade ethanol
(FGE ASTM D4806) or FGE / gasoline blend.
Dissolved O2 increases propensity for cracking

Sulfate SCC Surface initiated cracks in copper alloys in

sulfate solutions over many years.
 4.5. Environment Assisted Crac
Temp. Range (F) Affected metallurgy Not Affected

SCC occurs at metal temp All 300 Series are highly CS, LAS, 400
above 140F, increase in susceptible. series NOT
temp increases DSS more resistant. suscepible.
susceptiblity. NI alloys resistant, not
immune (Ni content 8-12% Ni alloy >35%
greatest susceptible) highly resistant
and > 45% near
immune

All metals and alloys.

 Carbon steel, low alloy steel & Ni alloys are
300 SS are susceptible more resistant

Any Temperature Some Cu alloys in aqueous 90-10 CuNI and

NH3 or NH3 compunds 70-30CuNi are
(Brasses Cu-Zn including nearly immune
admiralty and Al-brass are
susceptible) 300 SS and NI
CS in anhydrous NH3 alloys immune

Many common used matls i.e.

Carbon steel, low alloy steel,
high strength steel, 300 SS, Ni
base alloys, Cu alloys, Al
alloys, Ti alloys
CS, LAS, 400 SS + Precip Effect
Hardenable (PH) SS and some pronounced from
high strength NI base alloys amb temp to
300F (149C), but
decrease with
increasing temp

All CS susceptible Not SCC but

general corr in
some Al and Cu
alloys and
adverse effect on
non metal

Some Cu alloys (admiralty) 90/10 and 70/30

brass more susceptible CuNi more
resistant
Non-Copper
alloys immune
. Environment Assisted Cracking - All Industries
Affected Equipment
1) All 300 series piping and PV
components.
2) SCC seen in water-cooled
condensers & process side of
crude tower OH condsen.
2) Drains in HP units are
susceptible during start-up or
shutdown if not purged.
3) External Cl-SCC on insul
surfaces if wetted.
4) Bellows & tubing in H2
recycle streams with Cl
1) Rotating equpt - galvanic
couples b/w impeller and shaft
may cause pitting on shaft.
Pitting act as SR to cause
(transgranular) crack.
2) Deaerator cracking in late
1980's. Found that residual
stress, SR and deaerator
environ produced CF.
3) Cycling boiler- hundreds of
cold starts, DE cracks
magnetite, allowing corr.
Critical Factors
1) No lower limit for Cl, bec always
potential to concentrate.
2) Heat transfer cond increase
susceptibility as Cl can concentrate, wet
dry cond conducive to cracking
3) SCC occurs above 2 pH, lower pH
cause uniform corrosion.
4) Stress may be applied or residual
5) DSS have improved resistance over
300 SS but not immune.
1) Cracking more likely in evnirons that
promote pitting under cyclic stress
(thermal, vibration, DE).
2) There is no fatigue limit in CAF.
3) Corrosion promotes failure at lower
stress and no of cycles than endurance
limit.
4) Crack initiation sites incl pits, notches,
surface defects, fillet welds, changes in
section.
1) CE found in Eqpt handling
caustic, H2S & mercaptan
removal units, eqpt that uses
caustic for neutralization in
sulfuric and HF alkylation
units.
2) Failures occured in improper
heat traced pipe & eqpt,
heating coils.
3) CE occur due to steam
cleaning in caustic service.
3) Traces of caustic can conc in
BFW and cause CE of boiler
tube in wet and dry cond due
to overfiring.
1) Cu-Zn alloy tubes in HE +
NH3 may be as contaminant
or added as neutralizer.
2) CS is used in NH3 storage
tanks, pipign & eqpt in refrg &
some LO refining process.
1) In a fire molten metals may 1) LME occurs in very specific comb of
drip or contact with susceptible metal and low MP metals e.g. Zn, Hg,
matl like Zn galvinzing, Cd
electrical housing, melted Cu. 2) Very small quantity of molten metal
2) LME couples (SS300 rub with sufficient to cause LME w/o high TS.
galv steel, In refinery, Hg is
found in crude oils can
condense embrittling brass,
alloy 400, Ti or Al HX comp.
3) LME of Al comp occurred in
LNG and cryogenic gas plant
due to condensing liquid
mercury.
1)Susceptibility is function of caustic
conc, temp and stress level.
2) if conc mecanism present, conc of 50
- 100 ppm sufficient for cracking.
2) Stresses (approaching YS reqd) can be
residual or applied. PWHT is effective to
prevent SCC.
3) Crack progragation rate increase
dramatically with temp (can go thru wall
in hours during temp rise).
4) Special care with steam tracing &
steam out of non PWHT CS eqpt.
1) For Cu alloy: Zinc content of brass
affects susceptibility, as zinc incr above
15%. A water phase with NH3 or NH3
compoung must be present, pH >8.5,
residual stresses, occurs at any temp,
and O2 in traces reqd.
2) For Steel: anhydrous NH3 with <0.2%
water cause cracks in CS, SCC reported
at -33C in lab test, PWHT eliminates
susceptibility of most steels (TS <70
ksi), contamination with O2 increases
tendency, high residual stress make
susceptible.
Cd, Pb, Cu and Sn.
3) TS promotes crack propagation rate,
crack may pass thru wall in seconds of
contact with LM
1) CS piping and vessels in wet 1) 3 conditions reqd i.e. H2 at critical
H2S services in FCC, HP,
amine, sour water if welds not susccetible to embrittlement, stress
PWHT.
2) Storage sphere made with
slighly HS steel more
susceptible.
3) High strenth bolts and
springs very prone (>150Ksi TS flaking) + CP
absorb H2 during electro
plating and crack)
4)Cr-Mo vessels in HP units
cracks at welds & HAZ when
hardness > 235BHN
1) Likely decrease by PWHT or
applying coating
2) Avoid design with local
tensile stress, use of lap seam
weld & cold working
1) Mostly HX tubes in OH
distillation systems with
sulfates.
2) Damage observed in Crude
tower OH HX
conc in metal, micro structure
above threshold
2) H2 can come from welding by wet
electrode / flux (delayed cracking) +
cleaning or pickling in acid + wet H2S
service or HF acid service + plating (H2
3) Thk wall components vulnerable, take
logner for H2 to diffuse out.
4) Umtemp martensite & pearlite more
susceptible than tempered martensite at
same strength.
5) CS severely H2 charged as lower
toughness.
1) Field observation: High stressed, cold
worked component with stress conc are
susceptible to cracking + cracking in
FGE ASTM D4806 with water content +
corr inhibitor effect not known.
2) Lab observation (SSRT): Dissovled O2
most imp in E-SCC, no cracking in
deaerated cond + max potential in water
content 0.1-0.45% by vol + blends of
FGE & gasoline with as low as 20% vol
FGE + galv coupling of old and new steel
increases E-SCC + Cl content increase
changes mainly from IG to TG
1) Process must contain sulfates, NH3 is
usually present in low conc.
2) Cracking occurs over many years e.g.
10-15 years to cause tube leak
Prevention
1) Use resistant matl (Duplex +
Nickel base)
2) When hydrotesting use low Cl
water and dry thouroughly and
quickly
3) Coatings under insulation
4) Avoid design where Cl can
deposit or stagnate
5) HT SR of 300 SS may reduce
residual stress possible but
sensitization problem incr
susceptiblity to PTASCC, distortion
and reheat cracking.
1) Rotating Eqpt: Modify corr
environ by coatings /inhibitors,
minimize galvanic effect, use more
CR material.
2) Dearators: Proper FW and
condensate chemical control +
minimize residual stress with PWHT
+ smooth weld contour.
3) Cycling boilers: Slow start-up to
minimize D-Exp and water
chemistry under control
Inspection / Monitoring
1) SB cracks can occur from process side or
under insul. Matl shows no visible signs of
corrosion.
2) SCC cracks have branches and visually
detected by craze crack appearance.
2) Metallog shows typical transgranluar
cracks but IGC of 300 SS also seen.
3) Welds in 300 SS have ferrite (duplex
structure) more resistant to CL-SCC.
4) Fracture surfaces have brittle appear.
5) Surface cracks may be visually seen. PT or
phase analysis EC preferred methods.
6) Extremely fine cracks difficult to find with
PT. Polish or HP water blast may be required.
6) UT (RT not sensitive to detect fine cracks,
but at advanced stage)
1) CF fracture is brittle, Transgranular as in
SCC but not branched, multiple cracks
2) Cracking shows Little plastic deform at final
fracture.
3) In cycling boiler, crack on water side of
buckstay attach weld with waterwall, circular
pattern, bulbous in x-section.
4) in sulfidizing environ, cracks filled with
sulfide scale
5) Rotating Eqpt: UT + MT for crack detect
6) Deaerators: WFMT, tight cracks
7) Cycling boilers : buckstays, UT or EMAT
1) Cracking effective prevented by
PWHT of CS @10050F (repair
welds, int / ext attach welds)
2) 300 SS little advantage over CS,
Ni alloys more resitant at higher
temp or caustic conc.
3) Avoid steam out of non PWHT
CS, water wash first, use LP steam
for short periods.
4) Injection sys design reqd to
ensure caustic properly dispersed
before entering HT crude preheat
system
1) For CU alloys: Cu-Zn alloys show
improved resistance as Zn content
decr <15%, 90-10 CuNi & 70-
30CuNI nearly immune, SCC in
steam service controlled by
preventing ingress of air, 300 SS &
Ni alloys are immune
2) For CS: SCC prevented by adding
0.2% min water to NH3 (consider
vap phase < 0.2%), PWHT, use low
TS steel (<70 ksi) , weld hardness
<= 225BHN, prevent ingress of O2
in storage facilities
1) LME only prevented by
protecting metal from coming into
contact with low melting metal e.g.
do not weld galv steel to 300 SS
and protect from zinc coating
overspray.
2) Once cracking initiated from
LME, grinding out affected area is
not an acceptable fix.
1) Cracking typically parallel to weld in base
metal, but also in weld or HAZ.
2) Pattern is spider web of small cracks, which
initiate at weld flaws.
3) Cracks confirm by metallography as SB
intergrannular, typical occur in as-welded CS
and fine, oxide-filled.
3) Cracking in 300 SS typical transgranular
and difficult to distinguish from Cl-SCC.
4) Crack detection best by WFMT, EC, RT or
ACFM (surface prep by blasting reqd).
5) PT not effective for scale filled cracks and
should not be used singly.
6) Crack depth by SWUT + AET for Crack
growth.
1) For Cu alloys: Surface breaking cracks may
show Bluish Corrosion product. HX tubes show
single or branched SB cracks, can
intergranular or transgranular.
a) Monitor pH and ammonia of water to assess
susceptibility of Cu alloys.
b) HX tubes EC or visual insp, rolled area
susceptible
2) For CS: Non PWHT & HAZ, primarily
intergranluar.
3) WFMT welds in tanks, Ext SWUT using
TOFD, AET.
1) ME appears as brittle cracks in other wise
ductile material, confirm only by
Metallogarphy, Intergranular cracks filled
with LM metal.
2) Spectrographic analysis to confirm molten
metal species.
3) Detect crack by MT for ferritic steel and PT
for 300 SS and Ni
4) RT used to locate Hg deposits in HX tubes
bec of high density
1) Use LS steels and PWHT to
temper microstructure, reduce
hardness & stresses, improve
ductility.
2) Use low H2 dry electrodes, bake
out metal 400F or higher to diffuse
H2.
3) Heavy wall vessel requires
control s/d & s/u procedures to
cotrol pressursation sequence.
4) Apply lining, SS cladding to
prevent surface H2 reactions in
corrosive aqueous serivce.
1) CS storage tanks, piping & eqpt
+ transportation pipeline of FGE.
2) E-SCC not reported in FGE
manufacturer eqpt and tanks or in
transportation eqpt (barges, trucks,
railcars) + FGE blended with
unleaded gasoline (10% vol)
1) Life of HX tubes lengthened by
cleaning 1/5 years but ltd publish
info available.
2) 90/10 and 70/30 CuNI resist to
NH3 SCC also resistant to sulfate
SCC.
3)
1) HE crack can intiate SSF, but mostly SB.
2) Locations at high residual and tri-axial
stress and conducive microstructure e.g. HAZ.
3) On macroscale little evidence, some matl
show brittle fracture + in HS steels, cracking is
often intergranular.
4) For surface cracks PT,MT,WFMT, UT
5) RT not sensitive to HE cracks
6) if source of H2 is low temp aq envir, H2 flux
can be monitored with special instruments.
1) SCC appears as cracks in vicinity of welds
(parallel or transverse to welds) + cracks tight
and may be filled with corr product.
2) Cracks branched & IG, but TG or mixed
mode also reported, increased CL content
shifts from IG to TG.
3) Microstructure of metal subject to SCC are
ferrite or ferrite + pearlite.
4) WFMT preferred method, difficult to detect
by VT tight cracks filled with corr product.
5) SWUT where WFMT not feasible + ACFM
with less surface prep as in HAZ.
6) ECT not proven.
1) Tubes show single or branched surface
cracks, cause slow leaks (not rupture).
2) By metallogrpahy, branched TG cracks
difficult to distinguish from NH3 SCC.
3) Inspect tubes for cracks by EC or VT
4) Bending sample of tubes to detect shallow
initial cracks
Related Mechanism

Caustic SCC & PASCC

Mechanical fatigue
and Vibration induced
fatigue
Amine cracking &
Carbonate cracking
simlar forms of
alkaline SCC.

NA

LME also called Liquid

Metal Cracking (LMC)
Ni alloys are
susceptible to Ni-Ni
sulfide eutectic that
forms at 1157F
Also known as H2
flaking, underbead
cracking, delayed
cracking, H2 assisted
cracking, HIC.
Sulfide SCC & H2 SCC
in HF closely related
form of H2
embrittlement

Similar to other
reported in methanol
and various alkaline
aq
solutions

NA
Corrosion Description
Mechanism
Amine Corrosion General and/or localized corr principally on CS
in amine treating processes. Corrosion is not
caused by amine, but from dissolved acid
gases (CO2 and H2S), amine degradation
products, Heat Stable Amine Salts (HSAS) &
contaminants.

Ammonium Aggressive corrosion in hydroprocessing

Bisulfide Corrosion reactor effluent streams and in units handling
(Alkaline Sour alkaline sour water (Localized corrosion.)
Water)

Ammonium General or localized corrosion, often pitting,

chloride corrosion occurring under ammonium chloride or amine
salt deposits, often in the absence of a free
water phase.
Hydrochloric acid HCL (aq. HCL) causes both general and
corrosion localized corrosion. Damage in refineries is
most often dew point corrosion as vapors
containing water & HCL condense from
overhead stream of distillation, fractionation
or stripping tower. First droplets can be highly
acidic (low pH) and give high CR.

High temperature Presence of H2 in H2S streams increases

H2 / H2S corrosion severity of high temperature sulfide corrosion
above about 500F. This form of sulfidation
results in uniform thk loss in hot circuits in
hydroprocessing units.

Hydrofluoric (HF) HF acid can result in high rate general or

Acid Corrosion localized corrosion and may be accompanied
by hydrogen cracking, blistering and/or
HIC/SOHIC
Napthenic Acid High temperature corrosion that occurs
Corrosion (NAC) primarily in crude and vacuum units, and d/s
units that process certain fractions or cuts that
contain naphthenic acids ( hot dry HC that do
not contain free water phase).

Phenol (Carbolic Corrosion of carbon steel can occur in plants

acid) Corrosion using phenol as solvent to remove aromatic
compounds from lubricating oil feedstocks.

Phosphoric Acid Phosphoric acid is used as catalyst in

Corrosion (PAC) polymerization units. It can cause both pitting
and localized corrosion of carbon steels
depending on water content.
Sour Water Corrosion of steel due to acidic sour water
Corrosion (Acidic) containing H2S at pH 4.5 to 7.0 (CO2 may also
be present)

Sulfuric Acid SA promotes general and localized corrosion of

Corrosion CS and other alloys. Carbon steel HAZ may
experience severe corrosion.

Aqueous Organic Organic compounds in some crude oils

Acid Corrosion decompose in crude furnace to from low MW
organic acids which condense in distillation
tower OH systems and contribute siginificantly
to aq corrosion
 5.1. Uniform or Localized Loss in T
Temp. Range (F) Affected metallurgy Not Affected

CR increase with temp, Primarily carbon steel. 300 Series SS are

particularly in rich amine. highly resistant.
Temp above about 220F
(104oC) can result in acid
gas flash and severe
localized corrosion if
pressure drop is high
enough.

NH4HS salts precipitate in CS is less resistant. 300 Series SS,

reactor effluent streams + AL HX tubes highly DSS, Al alloys
when temp drop to 120 to prone to erosion corrosion and Ni alloys are
150F more resistant,
(depends on
NH4HS conc and
velocity).

Salts precipiate above All common materials

water dewpoint 300F, CR susceptible, increasing
increase with incr resistance: CS, LAS,
temperature. 300 Series SS, Alloys 400,
DSS, 800, and 825, Alloys
625, C276 and Ti
 All common materials Alloy 400, Ti and
used in refineries some Ni base
alloys have good
resistance to
dilute HCL.
(Ti performs well
in oxidiz
conditions)

Temperature above about Increasing resistance:

500 F. Increases with carbon steel, low alloy
increase in temp and H2S steels, 400 Series SS, and
conc. 300 Series SS.

High corrosion rates CS, Cu-Ni alloys, Alloy 400 Ni base alloys
observed > 150F LAS, 300 SS and 400 SS e.g. Alloy C276
are susceptible to used
corrosion / cracking and
generally not suitable for
HF service
NAC occurs hot stream Carbon steel, low alloy Alloys with
>425F, but reported as steels, 300 SS, 400 SS and increasing Mo
low as 350F. nickel alloys. show better
resistant with
Severity increase with min 2 - 2.5%
temp up to 750F, but NAC depending on
reported in hot coker gas TAN of crude
oil stream up to 800F

Corrosion minimal below Increasing resistance:

250F carbon steel, 304L, 316L
and Alloy C276.
CS and 304/304L SS
corrode rapidly above
450F

CR Increase with Incr in Increasing resistance:

temp carbon steel, 304L SS,
316L SS and Alloy 20.
Primarily affects carbon SS, CU alloys and
steel Ni alloys are
usually resistant.

Increasing resistance:
Carbon steel, 316L SS,
Alloy 20, HSCI, high nickel
CI , Alloy B-2 & Alloy C276.

All grades of carbon steel Most CR alloys

are affected crude tower OH
system not
affected
1. Uniform or Localized Loss in Thickness - Refining
Affected Equipment Critical Factors

1) H2S, CO2 and mercaptans 1) AC tied to operation of unit. CS is

removal units + crude, coker,
FCC, H2 reforming,
hydroprocessing, and tail gas
units.
2) Regen reboiler &
regenerator at high temp+
lean/rich HX, hot lean amine
piping, hot rich amine piping,
solution pumps & reclaimers
are prone to corrosion
suitable, but problem due to faulty
desing or operation.
2) Most to least aggressive: MEA, DGA,
DIPA, DEA, MDEA
3) Lean amine sol not corrosive (low
cond, high pH), but HSAS > 2% can
increase CR.
4) Lean amine sol contain H2S to
maintain stable FeS film.
5) H2S, NH3, HCN accelerate corr in
ROHC and piping.
6) High vel & turb cause local thick loss,
For CS limit 3-6 fps (rich amine) and 20
fps (lean amine)

1) HP Units : NH4HS salts 1) Below 2% wt NH4HS conc, soln not

precipitate in reactor stream at generally corrosive, above 2% incr
120-150F + fouling and vel corrosive with incr velocity.
corrosion at air cooler header 2) in HP & FCC reactors, coker furnace N
box, piping. converts to NH3 & reacts with H2S to
2) FCC Units: NH4Hs < 2% wt form NH4HS, at 150 F it precipitates
but vel & cyanides may from gas stream cause fouling / plugging
remove protective FeS if not washed.
3) SWS + Amine units: High 3) NH4HS salt deposit cause under
conc of NH4HS in stripper OH deposit corrosion & fouling.
piping, condenser, accumulator 4) O2 & Fe in wash water can lead to
4) Delayed Coker: High conc in corrosion & fouling in HP reactor
gas conc plant d/s.

1) Crude Tower OH: Tower top,
top trays, OH piping and HX
face Nh4 and amina salts
condensing from vapor phase.
2) HP reactor + Catalytic
Reformer + FCCU + Coker :
Effluent stream NH4CL salt
fouling and corrosion.
1) NH4CL salts may precipitate when
cooled in hot streams and corrode piping
& eqpt even > water DP 300F.
2) NH4CL salts are hygroscopic and
small water cause high CR > 100mpy.
3) NH4CL and amine hydrochloride form
hihgly corrosive acid soln with water.
1) Crude unit: In atmosph
tower OH system, HCl corr
occurs as firsr water drop (low
pH) condense from vap outlet.
2) HP units: Cl may enter as
organic chloride in HC feed or
recycle H2 and react to form
HCL + NH4CL salts can form in
effluent side as boht HCL &
NH3 present.
3) Cat reforming unit: Cl may
strip from catalyst, form HCL
which affect effluent d/s eqpt.
1) Corrosion severity increase with HCL
conc and temp.
2) Aq HCL can form beneath NH4Cl or
amine hydrochloride salt. HCL gas is not
corrosive, but with water forms HCL acid.
3) CS and LAS subject to high corr when
exposed to any conc of HCL at pH < 4..
4) 300 SS and 400SS not usefully
resistant at any con or temp.
5) Oxidizing agents (O2, Ferric, Cuprici
ions) increase CR particulary for Alloy
400 & B-2 (not Ti).
6) Ti fails rapidly in dry HC service.

1) Piping & eqpt in HT H2 / H2S
streams incl all HP units e.g.
desulf, hydrotreaters and
hydrocracking units
2)CR increase downstream of
H2 injection points.
1) Sulfidation rate increase with incr H2S
content and increasing temp.
2) CR in gas oil desulfurizer and
hydrocracker than naptha desulf by
factor of 2.
3) Chorium content improves resist but
when upto 7-9Cr.
4) Cr containing Ni alloys similar to SS
wil same CR.

1) Piping and equipment in the 1) CS forms protective Fl scale in dry

HF alkylation unit, flare piping conc acid. Loss of scale by vel, turb
& d/s units exposed to acid causes high CR.
carryover. 2) Presence of water can destablize Fl
2) Most eqpt of CS except HF scale to non protective scale.
acid regen tower and acid relief 3) Primary concern is HF-in-water conc of
neutral vessel of Alloy 400 . acid phase
3) High CR in eqpt > 150 F 4) Typical HF alkyl unit oper with 1-3%
condesing vapors off top of water in acid i.e. 97-99% HF-in-water at
Isostripper, Depropanzier, HF 150F at which CS is used.
stripper. 5) CR incr with incr temp and decr HF
4) Severe fouling by FeF conc (incr water)
product in piping, HX and top 6) RE in CS affect CR i.e. C, Cu, Ni, Cr i.e.
of Isostripper and Depropanizer Base / weld metal < 0.15% wt.
tower 6) O2 contamin increase CR of CS and
SCC of Alloy 400
1) Crude and vacuum heater
tubes & transfer lines, Vac
botm piping, AGO circuits;
HVGO and sometimes LVGO
circuits. also reported in the
LCGO and HCGO streams on
delayed coking units
processing high TAN feed.
2) Piping sys susceptible in
high vel & turb (welds +TW)
and CDU and VDU internals
corrode in flash zones by high
vel droplets
Phenol extraction facilities in
lubes plant.
1) Piping and equipt in
polymerization unit where
water mixes with catalyst
2) Corrosion in low velocity
area with no circulation e.g.
piping manifold, bottom of
kettle-type reboiler, partial
penetration welds, HX where
sufficient time to permit
settling of acid droplets.
1) Neutralization num or Total Acid
Number (TAN) of crude is measure of
acidity (organic acid content) as per
ASTM D-664.
2) TAN may mislead due to family of
acids & boiling points. NAC depend on
acidity of stream not crude.
3) S promote Fes and inhibits NAC upto a
point. NAC is particular prob with low S
crude & TAN ~ 0.10.
4) Corrosion most severe in two phase
flow, high vel or turb and hot vapor
condensing in distill towers.
1) Corrosion can occur in recovery
section where spent phenol is separated.
2) Dilute soln (5-15% phenol) are very
corrosive in extract dryer cond.
3) High vel promote localized corrosion.
1) CF conc, temp and contaminants.
2) Solid Phos acid catalysts are not
corrosive to CS, cause severe corr with
water.
3) Corrosion can penetrate 1/4" thk steel
tube in 8 hrs.
4) Most Corr probably during water-
washing oper at S/D.
5) Cl can increase PAC
Concern in OH systems of FCC
and coker gas fractionation
plant with high H2S and low
NH3 level
1) SA alkylation units and
waste water treatment plants.
2) Area of Alkylation unit
reactor effluent + reboiler, DIB
OH system+ Caustic treating
sections + Bot of fractionation
towers
1) All CS piping & eqpt in crude
tower, vacuum tower, and
coker OH system incl HX,
towers and drums.
2) Corrosion occur where water
accumulates or water droplets
impinge and turbulent areas
e.g. Botm of OH HX, boots of
separtor drum, elbows, tees,
d/s of CV.
1) H2S conc in sour water depends on
H2S pp in gas, temp and pH.
2) At given press, H2S conc in sour water
decr as temp incr.
3) Increasing conc of H2S decrease pH,
below 4.5 pH corr is concern.
4) Above 4.5 pH, thin sulfide layer limts
CR or sometimes can promote pitting
under deposit.
5) HCL & CO2 lower pH, NH3 incr pH
significantly results in alkaline sour
water and NH4HS corrosion.
6) Air or oxidant increase CR and
produce pitting or underdeposit attack.
1) CS CR increase significantly if vel > 2-
3 fps or acid conc < 65%.
2) Mix point with water release heat and
high CR where acid diluted.
3) Oxidizers greatly increase CR.
1) Low MW acids incl formic, acetic,
propionic and butyric acid.
2) Formic and acetic acid are most
corrosive, soluble in naptha, once water
condenses lower the pH.
3) Presence may be masked by other
acids HCL, H2SO4, H2CO3 etc.
4) Type and quantity of organic acid in
OH system are crude specific, one
source is decompose of napthenic acid in
crude.
5) Light OA not as corrosive as IOA. To
calculate HCL equivalent factor, multiply
OA ppm-wt by the factor, result will be
equivalent content of HCl (in ppm).
Prevention
1) Proper operation is most
effective way to control corrosion,
temp should not exceed limits.
2) Avoid buildup of HSAS.
3) Control local press drop to
minimize flashing, upgrade to 300
or 400 SS internals in absorber and
regnenerators.
4) O2 in leak causes HSAS
formation and hihg CR.
5) Fileter solids and HC with amine
sol.
Careful design when NH4HS
concentrations increase 2%wt &
above 8%wt + maintain velocity 10
to 20FPS for CS + use alloy 825 &
DSS when vel > 20FPS + Water inj
to dissolve NH4HS + for SWS use Ti
& Alloy C276
1) Limiting salts and chlorides
through desalting and / or adding
caustic + water wash to flush salt
deposits, + filming amine inhibitors
or neutralizations
Inspection / Monitoring
1) CS & LAS suffer uniform or localized
thinning, localized underdeposit attack +
Thinning will be localized for high vel.
2) Visual , UT for internal and UT scans or
profile radiography for external.
3) Corrosion coupons and/or corr probes. +
Montg should target hot areas unit.
4) Fouling of HX and filters can be sign of
corrosion problem
1) General thk loss in CS + Localised corrosion
at bends conc > 2% by wt
2) low vel cause under deposit corr by NH4Hs
satls
3) HX tubes fouling + corrodes admiarility
brass and Cu tubes.
4) sample to determine NH4HS concentration
5) UT and profile RT of high and low velocity
areas
6) IRIS, RFEC, MFL of air cooler CS tubes and
EC of SS tubes
1) Salts have whitish, greenish or brown
appearance. Water washing or steamout
remove deposits so fouling may not be evident
during visual inspection.
2) Corr under salts is very localized and results
in pitting.+ hihg CR.
3) Loaclised corrosion difficult to locate + RT
or UT thk for wall loss + Montg of feed streams
and itentifying dew point temp and later temp
monitoring, + Corrosion probes or coupons are
useful but salt must deposit on probe
1) Crude units: Optimize crude
desalt oper to reduce Cl (to 20 ppm
or less in OH accumulator water) +
Upgrade to Ni alloys + Ti tubes will
solve OH conden problem + caustic
injection d/s of desalter to reduce
HCL + NH3 & neutralizing amine
injection in tower OH line.
2) HP unit: Minimize water & Cl
salts carryover + minimize Cl ions
from H2 in catalystic ref + use Ni
alloy.
3) Catalytic Ref: Water wash HC
stream to remove Cl + special
absorbent in Cl bed to remove CL
from recycle H2
1) Damage minimized by using
alloys with high Cr content
2) 300 SS such as Types 304L,
316L, 321 and 347 are highly
resistant
1) CS oper > 150F check for thk
loss & upgrade to Alloy 400.
2) Careful operation of unit to
minimize water, O2, sulfur and
other contamnants in the feed.
3) Alloy 400 (solid or clad) be used
to eliminate the problems of
blistering and HIC/SOHIC. A SR to
minimize chance of SCC.
4) Alloy C276 used where there is
cracking problems with Alloy 400.
1) CS & LAS suffer uniform thinning, localized
corr or underdeposit attack.
2) 300 and 400 Series SS will often suffer
pitting attack and 300 Series SS Cl-SCC.
3) Serious corr found at mix points where dry
Cl contain stream mix with water saturated
stream or cooled to DP.
4) LTA detection by UT scan or profile RT
4) pH of water in atmosph tower OH
accumulator checked every shift. Cl & Fe
check less frequently.
5) Water phases in other units also check
periodic sampling from OH durm of fract or
stripping tower.
6) Probes or coupons and/or coupons for rate
and extent of damage.
1) Uniform thk loss and FeS scale formation
(scale is 5 times volume of metal loss +
tightly adherent gray scale)
2) UT, RT, VT for metal loss.
3) Oper temp field verification against deisgn
temp + Process simulation checks for H2S
levels
1) Localized general or severe thinning of CS
+ Cracking due to H2 Stress cracking
blistering and/or HIC/SOHIC damage.
2) Fouling due to iron fluoride scales.
3) Alloy 400 shows uniform thk loss but not
significant scaling.+ susceptible to SCC in
moist HF vapors in presence of O2.
4) UT and RT are used for thk loss.
5) Programs to monitor small bore piping,
flange face corrosion, blistering and
HIC/SOHIC as per API RP 751.
6) Monitor RE of CS & inspect for localized /
preferential corrosion of welds as per RP 751.
1) blending crude to reduce the
TAN and/or increase the sulfur
content, upgrade metallurgy or
chemical inhibitors.
2) For severe conditions, Type 317L
SS or other alloys with higher Mo
may be required.
3) HT NAC inhibitors used with
moderate success but effects on
d/s catalyst to be assessed.
1) Best prevented thru proper matl
selection and phenol solvent
chemsitry control.
2) OH piping designed for max
velocity of 30fps in recovery
section and maintian temp atleast
30F above dewpoint.
2) 316L may be used in top of dry
tower, phenol flash tower, that
handle phenol-water.
3) Alloy C276 for high vel area
where 316L inadequate
1) Selective upgrading to CR
materials is only option where
water cannot be eliminated.
2) Type 304L satsifactory in 100%
conc upto 120F, 316L feqd from
120F to 225F.
3) Type 316L SS and Alloy 20
effective at concentrations up to
85% at boiling temp.
1) NAC is localized, pitting corrosion, or flow
induced grooving in high vel areas.
2) In low velocity condensing conditions, alloys
including CS, LAS & 400 SS may show uniform
thk loss and/or pitting.
3) UT, RT for thk loss.
4) Monitor TAN and sulfur content of crude
charge and side streams to determine the
distribution of acids in the various cuts.
5) Corrosion Montg (ERP & Coupons) + + H2
probes.
6) Monitor streams for Fe & Ni content
1) General or localized corrosion of CS.
2) Erosion-corrosion or condensation corr
observed in tower overhead circuits.
3) UT and RT to monitor thk loss.
b) ER probes and corrosion coupons.
1) General or localized thinning of CS.
2) UT and RT for loss of thickness.
3) Sample iron in water from first column OH
receiver.
3) Online ER probes and/or corrosion coupons
in water draw from first column OH condenser
and reboiler.
1) 300 SS can be used at temp <
140F as Cl-SCC not likely.
2) Cu and Ni alloys generally not
susceptible to ASWC but Cu alloy
vulnerabel to corrosin with NH3.
1) Corrosion minimized thru
materials selection and oper within rapidly (attacks weld slag).
design velocities.
2) Alloys such as Alloy 20, 904L and stagnant areas such as in storge tanks or rail
C-276 resist dilute acid corrosion
and form a protective
iron sulfate film on the surface.
3) Acidic streams can be washed
with caustic to neutralize acid.
1) Corrosion by LOA in crude OH
system can be minimized by
injecting neutralizer but problem
with changes in crude blend.
2) Filming amines can prevent
corrosion if it doesnt react with OA,
but it is not as effective as
neutralization.
3) Upgrading to CR alloy
1) Corrosion is typical general thinning, but
localized corrosion or underdeposit attack can
occur, if O2 is present.
2) Corrosion in CO2 containing environs may
be accompanied by carbonate SCC
3) 300 SS are susceptible to pitting attack and
crevice corrosion and/or Cl-SCC.
4) UT scan & Profile RT for LTA.
5) Process and Corrosion montg, measure pH
of water from OH accumulator
6) Properly placed corrosion probes + coupons
provide rate and extent of potential damage.
1) General corrosion but attacks CS weld HAZ
2) H2 grooving may occur in low flow or
cars.
3) If CR & vel high, there will be no scale.
4) Corr of steel by dilute acid is usually overall
metal loss or pitting, becomes severe with
increasing temp & vel.
5) UT or RT inspection of turbulent zones and
hottest areas.
6) Coupons and ER probes.
1) Light OAC leaves surface smooth and
difficult to distinguish from HCL corr.
2) In significant flow, surface smoothly
grooved.
3) UT and RT inspection for thk loss, LRUT for
long pipe run.
4) For CS, damage is general thinning or
hihgly localized where water condenses.
5) Process monitoring for pH and water
analysis in crude tower OH drum for OA.
6) Corrosion probes and/or coupons.
Related Mechanism

Amine stress
corrosion cracking

Erosion , Erosion-
Corrosion

HCL Corrosion,
Chloride SCC and
Organic acid
corrosion of tower OH
system
Ammonium chloride
corrosion + Chloride
SCC and Organic acid
corr of distillation
tower OH systems

High temperature
sulfidation in the
absence of H2

Environmental
cracking of carbon
steel and Alloy 400
can occur in HF. R+
Hydrogen stress
cracking in HF +
blistering and
HIC/SOHIC damage.
Sulfidation is
competing
mechanism mostly
with NAC. Where
thinning occurs, it is
difficult to distinguish
NAC & Sulidation.

Not Applicable

Not Applicable
Wet H2S damage and
Carbonate SCC

Not Applicable

Damage difficult to
differentiate from HCL
corrosion.
Amm Chloride
corrosion and
Chloride SCC also
related.
Corrosion Description
Mechanism
Polythionic Acid SCC normally occuring during S/D, S/U or
Stress corrosion during operation when air and moisture are
cracking (PASCC) present. Cracking due to sulfur acids forming
from sulfide scale, air & moisture acting on
sensitized Aust SS (adjacent to welds or high
stress areas). SCC may propagate rapidly (min
or hrs).

Amine stress Amine cracking is common term applied to

corrosion cracking cracking of steels in aqs alkanolamine systems
used to remove H2S and/or CO2 and mixtures
from various gas and liquid HC streams. It is
most often found in non PWHT CS welds or
cold worked parts.
Wet H2S Damage Four types of damage:
(Blistering / HIC / a) H2 Blistering: . H atoms form during
SOHIC / SSC) sulfide corrosion, diffuse into steel, and
combine to form molecule at lamination or or
inclusion, too large to diffuse out & press
builds to deform metal as surface bulges on
ID, OD or within wall thk.
b) HIC: Adjacent blisters at different depths
develop cracks, that link them, have stair step
appearance refer to as "stepwise cracking".
c) SOHIC: Similar to HIC but more damag
form of cracking, appears as array of cracks
stacked on top of each other. Result is thru thk
crack perpendicular to to surface driven by
high sress (R or A). Appear in HAZ initiating
from HIC or SSC.
d) SSC: Form of HIC result from absorption of
atomic H2 produced by sulfide corr. It can
initiate on surface at high hardness zone in
weld metal (cover pass not temp) and HAZ.
PWHT is beneficial to reduce hardness and
residual stress. Use preheat helps minimize
hardness problems.

Hydrogen Stress Environmental cracking that can initiate on

Cracking - HF surface of carbon steel and HSLA with
localized zones of high hardness in weld metal
and HAZ as result of exposure to aqueous HF
acid environ.
Carbonate Stress Surface breaking cracks occur adjacent to CS
Corrosion Cracking welds under the combined action of tensile
(ACSCC) stress and corrosion in systems containing free
water phase with carbonate (some H2S also
present). It is a form of Alkaline SCC.
 5.1.2. Environment Assisted Cra
Temp. Range (F) Affected metallurgy Not Affected

300 Series SS, Alloy

600/600H and 800/800H.

Cracking has been Carbon steels & Low alloy

reported at ambient steels
temperatures with some
amines.

Increasing temperature
and stress level incr the
likelihood and severity of
cracking.
Blistering, HIC, and SOHIC Carbon steel and low alloy
damage have been found steels.
to occur between ambient
and 300F or higher.

SSC generally occurs

below 180F (hihger if Aq
phase of H2S).

Carbon steels & Low alloy Alloy 400 not

steels susceptible to
cracking but
prone to IG SCC
in non SR cond.
In CO2 removal units, Carbon steels & Low alloy
cracking may occur when steels
CO2 content is above 2%
& temp
exceed 200F (93C).
5.1.2. Environment Assisted Cracking - Refining
Affected Equipment
1) HE tubes, furnace tubes and
piping sensitized and in sulfur
environ.
2) FH burning oil, gas, coke
depending on sulfur levels in
the fuel.
3) FCC, hydroprocessing units
(heater tubes, hot feed/effluent
HX tubes, bellows), Crude and
coker units (piping).+ Boilers
and HT eqpt exposed to sulfur
combustion products
All non-PWHT carbon steel
piping and eqpt in lean amine
service including contactors,
absorbers,
strippers, regenerators and
heat exchangers as well as any
equipt subject to amine
carryover.
Critical Factors
1) combination is required of:
A-environment: metal form sulfide scale
exposed to sulfur comp. It reacts with
moisture and O2 to form sulfur acids
(PA).
B- metal must be in sensited cond.
C- stress Residual or applied
2) Sensitization refers to chromium
carbide formation in grain boundary of
metal in temp range 750 to 1500F.
3) Low C grades (<0.03%) are less
sussceptible and can be welded w/o
sensitization. L grades do not sensizie if
long term temp < 750F
1) Cracking more likely in MEA & DEA
but also found in MDEA & DIPA.
2) API RP 945 for PWHT requirement for
amine services.
3) Cracking most often in lean amine,
rich amine cracking due to wet H2S
problem.
4) Some refineries believe crack not
occur below amine conc 2-5% but steam
out can reduce limit to 0.2%.
1) 4 damage can occur in all 1) pH:
refinery where wet H2S H2 diffusion minimal at pH 7, HCN in
present. water incr permeation in alkaline water.
2) in HP unit, incr conc of Fav cond for damage:
NH4HS above 2% incr potential - >50 ppmw H2S dissolved in water
of Blistering, HIC and SOHIC in
- free water pH<4 and dissovled H2S
vapor recovery unit of FCC and- free water pH>7.6, 20ppmw doslvd
coker, fractionator tower, HCN and some dissolved H2S.
absorber & stripper tower, - >0.0003 Mpa (0.05 psia) partial
comp interstage separator, ko pressure H2S in gas phase
drum, HX etc prone bec of high- incr NH3 can >pH where cracking can
NH4HS conc. occur
3) SSC most likely in hard weld
2) H2S:
and HAZ, HS comp such as Arbitrary value 50 ppmw used for H2S
bolts, relief valve springs, 400
conc that cause problem but even 1
SS valve trim, compressor ppmw was found sufficient for H2
shaft, sleeves etc. charging of steel. Susceptibility to SSC
incr with incr H2S pp > 0.05 psi with TS
about 90 ksi or hardness > 237HB.
3) Temperature:
H2 charging potential incr with temp but
SSC potental max near amb temp.
4) Hardness:
Low CS should have weld hard < 200 HB
as per NACE RP 0472 (not suscept to
SSC unless hardness > 237 HB).
Blistering, HIC and SOHIC not related to
hardness.
5) Steel making:
HIC often found in diry steel. Steel
chemistry and manuf tailored to make
HIC resistant in NACE Pub 8X194 (but
1) Eqpt exposed to HF acid at 1) Susceptibility incr with increasing
any conc and hardness above hardness > 237 HB highly prone.
recomm limit. 2) Cracking may occur rapidly in hours
2) HSLA (ASTM A 193-B7) bolts after exp to HF environment.
and compressor components. 3) Hard microstructure may form in low
3) B7M bolts if overtorqued heat input welds, HAZ, in LAS or
inadequate PWHT
1) Most prevalent in FCCU Main
fractionator OH condensing &
reflux system
2) SWS units in pump around
return line to SWS tower, OD of
cold worked SA-179 cond tubes
3) Piping and eqpt in potash
carbonate in Catacarb and CO2
removal units.
1) Residual stress level of CS and water
chemistry are critical factors. Usually
occurs at welds or cold work area not
stress relieved.
2) Water chemistry: Liq water phase
present + pH of sour water 8-10 + H2S
also present + Increasing NH3 and
decreasing H2S increase likelihood +
Carbonate ion above threshold conc >
100 ppmw + with or without cyanides
and polysulfide
3) FCCU feed quality and operation
affect cracking susceptiblity i.e. N2
higher in cases where ASCC occur +
cracking usualy in low sulfur feed +
mostly N/S ratio in feed of 0 to 70
4) In CO2 removal unit, cracking when
CO2 content > 2% and temp exceed
200F (93C).
Prevention Inspection / Monitoring

1) If eqpt to be opened, flush with 1) Typically occurs next to welds, but can also
alkaline or soda ash soln to occur in base metal (may not be evident until
neautralized sulfur acids during s/d a leak appears during s/u or in some cases,
or purge with N2, NH3 (refer NACE operation).
RP0170). 2) Cracking is INTERGRANULAR, corrosion or
2) For furnace, keep firebox above loss in thk is usually negligible.
dewpoint to prevent acid forming 3) PT used to detect PASCC after flpper disc
on tubes. sanding to remove tight deposit.
3) L grades SS 304L/316L/317L 4) PASCC is inspection challene bec crack may
sensitize if several hours above not occur until shutdown.
1000F or long term > 750F. 5) Montg for PASCC during operation not
4) Improved resistance with Ti & Nb practical bec condition not present.
stab grades e.g. SS 321, 347 and Ni
alloys 825, 625.
5) Thermal stab heat treatment at
1650F stab SS welds but diffic in
field.
6) Susceptiblity by lab corr test as
per astm A262 prac C.

1) PWHT all CS welds, repair welds
and attachment welds as per API
RP 945.
2) Use solid or clad SS Alloy 400 or
other CR alloys in lieu of CS.
3) Water wash non-PWHT CS prior
to welding, heat treatment or
steamout.
1) Surface breaking cracks primarly in weld
HAZ but also in weld & high stress areas.
2) Crack typically parelell to welds, but inside
weld transverse or long.
2) At Set on Nozzles cracks radial to BM and in
set in nozzle parallel to weld.
3) Appearance similar to H2S cracking
4) Positive ID by metallography i.e.
INTERGRANLUAR (Oxide filled, branched)
5) Crack detection best by WFTM, ACFM.
6) PT not effective for tight, scale filled cracks.
7) SWUT for crack depth (not branched), and
AET for crack growth.
1) Effective barrier that protect
steel sruface from wet H2S can
prevent damage including alloy
cladding and coatings.
2) A common practice to use wash
water injection to dilute HCN conc
in FCC gas plant or convert HCN to
harmless thio cynate by inject
ammonium polysulfie.
3) HIC resistant steel to reduce
blistering & HIC per NACE Pub
8X194.
4) SSC prevented by reducing
hardness of weld and HAZ to
200HB (Max) by preheat, PWHT,
WPS, and carbon equivalent (refer
to NACE RP 0472).
5) PWHT can minimize SOHIC but
not blistering and HIC.
6) Special corrosion inhibbitor.
1) PWHT reduce residual stress
and hardness.
2) Low strength CS with weld
hardness < 200HB (NACE SP 0472
susceptible if > 237BH).
3) Use CS with CE: <0.43.
4) B7M bolts are low strength and
softer than B7.
5) Cladding or non metallic
coatings for barrier to H2 diffu will
prevent cracking..+
1) H2 blisters appear as bulges on surface of
steel of PV, found rarely on pipe and very
rarely in middle of a weld. HIC can occur
wherever blistering or subsurface laminations
are present.
2) In PV, SOHIC and SSC damage is most often
associated with welds. SSC also be found
where zones of high hardness or in HS steel
components.
3)Process condition evaluated by PE and Corro
specialist to identify eqpt prone to H2S
damage.
3) Insp for H2S focusses on welds and nozzles
(detection and repair outlined in NACE RP
0296).
4) Crack detection best by WFMT, EC, RT or
ACFM technique. Surface prep usually not
required for ACFM.
5) SWUT especially useful for insp and crack
sizing. ER instruments not effective for crack
depth measuring.
6) AET used to monitor crack growth.
7) Grinding or gouging crack another method
to crack depht measure.
1) INTERGRANULAR, SB cracks, usually
associated with welds and confirmed by
metallography only.
2) WFMT for SB cracks.
3) Hardness measurement best method to
determine susceptibility.
4) High hardness zone in weld cover pass and
attacment welds (not tempered)
1) Post-fabrication SR heat
treatment of about 1200-1225F
as per WRC 452 proven method to
prevent ACSCC (for repair, int-ext
attachment welds).
2) Cracking can be eliminated with
barrier coatings, solid or clad with
300SS, use Alloy 400 in lieu of CS.
3) water wash non PWHT prior to
steam out or heat treatment in hot
carbonate service.
4) A Metavanadate inhibitor to
prevent cracking in hot carbon
system in CO2 removal unit.
1) Cracking typically paralell to weld in HAZ or
BM within 2" of weld.
2) Cracking may also occur in weld.
3) Patternn is spider web of small cracks +
INTERGRANULAR + very fine oxide filled
cracks similar to caustic SCC, amine SCC.
4) Cracks may be mistaken for SSC or SOHIC
but further away from weld toe.
5) Montg of pH of FCC sour water is fastest
and cost effective method to locate areas
prone to ACSCC.
6) Monitg of CO3- conc in sour water.
7) Crack detect best by WFMT or ACFM. PT
cannot find tight, oxide filled cracks and
should not be used.
8) SWUT for crack depth measure but ER
instrument not suitable due magnetic oxide in
crack.AET for crack growth.
9) Grinding out crack is viable method to
measure depth (cracks dont extend by
grinding)
Related Mechanism

Also know as
Polythionic Acid
Stress Corrosion
Cracking (PTA SCC),
Intergranular
Corrosion (IGC) and
Intergranular Attack
(IGA).

Amine stress
corrosion cracking is
a form of Alkaline
SCC. Caustic SCC and
carbonate SCC are
two other forms of
ASCC similar in
appearance.
SSC is form of H2
Embrittlement +
Amine cracking &
Carbonate crackign
are simlair and also
confused sometimes
with wet H2S
cracking

Same mechanism
that is responsible for
SSC in wet H2S
environ except that
HF acid generating
the H2
Amine cracking and
caustic stress
corrosion cracking are
to similar forms of
ASCC.
Corrosion Description
Mechanism
High temperature HTHA results from exposure to H2 at elevated
Hydrogen Attack temperatures and pressures. The H2 reacts with
(HTHA) carbides in steel to form methane (CH4) which
cannot diffuse through steel. Loss of carbide
causes an overall loss in strength.
CH4 pressure builds up, forming bubbles or
cavities, microfissures and fissures that may
combine to form cracks.
Failure can occur when cracks reduce the load
carrying ability of pressure part.

Titanium Hydriding Ti Hydriding is metallurgical phenomenon in

which hydrogen diffuses into titanium and
reacts to form an embrittling hydride phase,
result in complete loss of ductility with no
noticeable sign of corrosion or thickness loss.
 5.1.3. Other Mechanisms - Re
Temp. Range (F) Affected metallurgy Not Affected

Iincreasing resistance: CS, 300 SS, 5Cr, 9Cr

C-0.5Mo, Mn-0.5Mo, 1Cr-
0.5Mo, 1.25Cr-0.5Mo,
2.25Cr-1Mo, 2.25Cr-1Mo-V,
3Cr-1Mo, 5Cr-0.5Mo and
similar steels.
and 12 Cr alloys,
not susceptible to
HTHA at cond
normally in
refinery units.

Occurs above 165F (74C) Titanium Alloys

and at a pH below 3, pH
above 8 or neutral pH with
high H2S content + above
350F in absence of
moisture and O2
5.1.3. Other Mechanisms - Refining Indsutry
Affected Equipment Critical Factors

HP units, such as hydrotreaters 1) HTHA preceded with time period when

(desulfuriz) and hydrocrackers,
catalytic reformers, H2
producing and cleanup units,
such as pressure swing
absorption units, are all
susceptible. + Boiler tubes in
very high pressure steam
service.
no changes in properties is noted.
2) Incubation period is time during which
damage is enough to be measured with
insp techniques.
3) Cruves for temp, H2 pp and safe oper
limits for CS, LAS in API 941 (reasonably
conservative for CS up to 10,000 psi pp).

Primarily in sour water 1) Galvanic contact of Ti with more

strippers and amine units in active metal like CS and 300 SS promote
OH condensers, HE tubes, damage.
piping and Ti eupt operate > 2) Occurs over time as H2 absorbs and
165F & also above 350F (177C) reacts to form embrittling hydride, will
in the absence of moisture or contine until complete loss of ductility.
O2 + CP equpt with potential 3) Solubility of H2 in pure Ti and alpha-
values <-0.9v sce. beta alloys is limited (50-300 ppm) and
once exceeded hydride forms. Beta
alloys more tolerant up to 2000 ppm
Prevention
1) Use LAS with Cr and Mo to
increase carbide stability and
minimize methane formation, also
W & V stabilizer.
2) Norma 25F to 50F safety factor
approach when using APIRP941
curves.
3) Several failures of C-0.5Mo, so
its curved removed and not
recommended for new eqpt in hot
H2 service.
4) 300SS overlay or clad at H2
service if BM does not have
adequate sulfidation resist +
decrease in partial pressures for
outgassing in shutdowns
1) Ti should not be used in
hydriding cond e.g. in Amine and
sour water.
2) If galvanic contact promotes
hydriding, then use all Ti or
electrically isolate to avoid galvanic
couple ( may not prevent hydriding
in alkaline sour water
environments.)
Inspection / Monitoring
1) HTHA can be confirmed by special
techniques incl metallography.
2) H2/C reaction can cause surface. If C diff
limited, then internal decarb, methan
formation and cracking.
3) In early stage, bubbles / cavities can be
detected by SEM (difficult to distinguish with
creep cavities). Early HTHA only be confirmed
by metallogrpahy.
4) In later stage, fissures or decarb can be
seen by microscope of replica metall.
5) Cracking and fissuring are intergranular &
occur adjacent to pearlite (Fe carbide).
6) Some blistering due to molecular H2 or
methane in lamination visible by VT.
7) Damage occur in BM, weld and HAZ SO
INSPECTION IS VERY DIFFICULT.
8) UT with vel ratio and ABUT succesful to find
fissures or cracking only if damage reached pt
when microvoid visible at 1500X magnification
by microscope.
9) Bulging of cladding from BM is tell tale sign
that HTHA occured.
10) In-situ metallog can detect only micro
fissure, fissureing and decarb near surface
(but decarb may be due to HT).
11) Conventional WFMT and RT severely
limited in ability except advaced stage of
cracking. AET not proven method.
1) TiH is metallurigcal change and only can be
confirmed by metallurgical technique or
mechanical testing.
2) Quick test is bend or crush test in vice.
Nomral Ti deform in ductile fashion and
embrittled will crack / shatter with no ductility.
HX tubes will crack when tube bundle is
removed or reroll done.
3) Specialized ECT reported able to detect
hydriding damage.
4) No other techniques other than the
metallurgical or mechanical methods.
Related Mechanism

A form of HTHA can

occur in boiler tubes
and is referred to by
the fossil utility
industry as hydrogen
damage.

Hydriding is a unique
to a few materials
including alloys of
titanium and
zirconium.
Oxidation General >1000f - Iron-based
thinning CS >1500 - alloys Upgradin
with an 300SS g more
oxide layer resistant
covering alloy*
the surface

Sulfidation Hydrogen >500, Iron, nickel Add Cr

accelerates <500 for and copper
corrosion- copper based
Uniform alloys alloys
thinning
( localized
sometimes
)

Requires >1100F Iron-based Lower

Carburizati high alloys temp,
on carbon- higher
activity O2&S
gas, low partial
oxygen pressure
potential
Requires --- CS, LAS Add Cr, Mo
Decarburiz low
ation carbon-
activity
gas, CS will
be pure
iron.
Metal Preceded 900-1500 All No metal
Dusting by is immune-
carburizati H2S forms
on-pits protective
filled with sulfide
crumbly layer
residue of
oxides and
carbides in
LAS Deep
round pits
in SS
Fuel Ash All Injecting
Contamina special
nts are S, additives
Na,K,V-
Molten
dissolves
oxide layer
& 50 Cr-50
Ni more
resistant

Nitriding Its rare- CS, LAS, 30-80% Ni

Nitrogen Starts>600 300SS,
diffuses , severe 400SS
into >900
surface
forming
needle-like
particles of
Fe3N and
Fe4N hard
brittle
surface
layer dull
gray dry

Environme
nt-
Assisted
Cracking
Chloride Surface >140 F SS300 Use low
SSC, initiated chloride
cracks water
under the
combined
action of
tensile
stress,
temperatur
e and an
aqueous
chloride
environme
nt.
 Corrosion Initiate @ ---- All Design
Fatigue pits,
notches,
surface
defect.
brittle
fracture
,Transgran
ular, ,not
branched.

Caustic Surface ----- CS, PWHT, Ni

SCC cracks LAS,300 SS alloys are
( Embrittle adjacent to resistant
ment) non-PWHT-
welds-
Integranula
r spider
web and
filled
w/oxides-
Transgranu
lar in
300ss-50
to 100 ppm
is sufficient
for
cracking

Ammonia Copper Any range Copper PWHT CS-

SCC alloys: alloys CS 300SS, Ni
aqueous, alloys, 90-
8.5 pH, O2, 10/70-30
zinc>15%, CuNi are
bluish immune-
corrosion process
product, control
trans/inter
granular
cracks
CS-
anhydrous
ammonium
, <.2%
water,
Air/O2, non
PWHT weld
or HAZ
 Liquid Liquid ---300 SS All Prevented
Metal Metal -Zinc Cu by
Embrittlem Embrittlem Alloys protecting
ent (LME) ent (LME) -Mercury metal
is a form of Alloy 400 substrates
cracking -Mercury from
that results coming
when into
certain contact
molten with the
metals low
come in melting
contact metal.
with
specific
alloys.
Cracking
can be
very
sudden
and brittle
in nature.
Intergran
ular
cracking

Sour H2S --- CS SS,Cu

Water decreases alloys, Ni
(Acidic) pH to 4.5- alloys
general,
localized
pitting-SCC
may occur
in 300SS.

Sulfuric Affect CS- ---- All Ni alloys

Acid HAZ-
Severe
corrosion
in
CS@>3FPS
and/or
>65%
concentrati
on-
General
corrosion
General-
Environm
ent-
Assisted
Cracking
Polythionic Occurs 750-150 Sensitize Use
acid Stress during for austenitic chemically
CC (PASCC) shutdowns, sensitizatio steels stable steel
startups, n (321ss,
when 347, alloy
exposed to 825 and
air& alloy625)
moisture-
HAZ L
grade SS is
less
susceptible
to
sensitizatio
n-
Intergranul
ar cracks.

Amine Occurs in >ambient CS, LAS PWHT,

Stress CC lean Resistant
amines- alloys
MEA, DEA
mainly-
concentrati
on is not a
factor-
initiate ID
on welds
( transvers
e or
longitudina
l) or
adjacent to
HAZ-
Intergranul
ar and
filled with
oxides
 Wet H2S Caused by <180f Process Focus on
Damage atomic (pH, H2S weld seam
(Blistering/ hydrogen. below 50, and
HIC/SOHIC/ H 2 is wash nozzles-VT
SSC) formed due water, WFMT,
to ammonia EC,
corrosion. &cyanides RT/ACFM*
concentrati SWUT-
ons- PWHT Volumetri
c
inspectio
n& crack
sizing *

Hydrogen Results by --- PWHT, WFMT,

Stress exposure Resistant Hardness
Cracking- to aqueous alloys testing
HF HF acid
environme
nt- HAZ-
Interganula
r- use CS
with
Carbon
equivalent
(CE) <0.43

Carbonate >200F PWHT, WFMT,

Stress Susceptibili Resistant SWUT
Corrosion ty alloy
Cracking increases
with pH
and
carbonate
concentrati
on-
Propagate
parallel to
welds,
weld
deposits,
HAZ-
Intergranul
ar and
filled with
oxides

General-
Other
Mechanis
ms
HTHA Exposure --- CS, C-Mo, Add
to Cr-Mo Cr&Mo
hydrogen
at elevated
temperatur
es and
pressures-
H reacts
with
carbides to
form
methane-
300ss and
>5Cr are
not
susceptible
to HTHA-
may cause
decarburiz
ation-
Intergranul
ar with
blistering
sometimes
.

Titanium Hydrogen >165f, > Titanium Avoid

hydriding diffuses 350 in alloys titanium
into hydrogen alloys in
titanium to atmospher hydriding
form e. services
hydride
(brittle)-
PH<3,
PH>8
UT

UT

MG,
hardness
testing

FMR, MG,
hardness
test

VT*
,Heater
tubes-
Compress
ion wave
UT*
VT

Mg,
hardness
test, VT,
magnetism
(300SS)

PT, Phase
analysis
EC
technique
s*
UT,
MTWFMT

WFMT,EC,
RT
/ACFM,*P
T Not
Good

EC-
Copper
Alloys, CS-
WFMT,SWU
T & AET
MT,PT

UT,RT
,Corrosion
Probes

RT,UT, ER
probes
PT

ACFM/WF
MT,
PT(not
good)*
 UT
techniques

EC
Techniques