Refinery Materials and Corrosion

Stress Corrosion Cracking

2011

Stress corrosion cracking

overview

Stress corrosion cracking (also known as environment-assisted

cracking) is defined as brittle cracking of a susceptible material through
the combined action of a specific corrodent and tensile stress
Sources of stress
applied stresses from internal pressure, structural loading, or
thermal expansion
residual stresses from welding or forming
Common SCC mechanisms
chloride SCC
caustic SCC
amine SCC
polythionic acid SCC

Chloride SCC

description of damage and affected materials

Description of damage
surface-initiated cracks, typically with many branches that give the
surface a crazed-cracked appearance
usually little or no signs of other corrosion
fracture surfaces show little or no deformation
metallography typically reveals transgranular (across the grains)
cracks, but cracks can also be intergranular (between the grains)
Affected materials
most austenitic SS (3xx series) alloys are susceptible
duplex SS alloys are more resistant, but can crack at temperatures
over 300F (150C)

Chloride SCC
critical factors

Chloride content, temperature and pH (from API 581-2008)

Chloride SCC
critical factors

Chloride content
hydroblasting and hydrotest water should be limited to 50 ppm
chlorides
chlorides may become concentrated above the bulk stream
concentration in crevices, at heat-transfer surfaces, by alternating
wet-dry cycles, or at steam leaks
chloride sources include
chloride salts from crude oil
water condensed from process stream
steam/boiler feedwater
catalyst
insulation
organic chlorides

Chloride SCC
critical factors

Temperature
cracking typically occurs at temperatures above 140F (60C)
pH
cracking typically occurs at pHs between 2 and 10
Oxygen
dissolved oxygen normally accelerates cracking
Stress
cracking is usually associated with residual stresses from welding or
forming

Alloy Ni content
SS with Ni content of 8% to 12% is most susceptible to cracking
alloys with Ni content above 35% are highly resistant and above 45%
are nearly immune

low Ni duplex SS has better resistance than 3xx SS, but will crack at
higher temperatures

Chloride SCC

affected units or equipment

All 3xx SS alloy piping and pressure vessel components in any process
unit where chlorides are present
Crude tower overhead streams
Drains in hydroprocessing unit SS piping are susceptible to cracking
during startup/shutdown if not properly drained and purged

Water-side of water-cooled condensers

Bellows and instrument tubing, particularly those in chloride-containing
recycle hydrogen streams
External cracking of insulated surfaces, particularly near steam tracing
leaks

Chloride SCC

example: Penex stabilizer reflux pump 316 SS seal flush line

Penex (isom) unit stabilizer reflux pump seal flush

line, diameter x 0.049 inch (1.25 mm) wall, 316
SS tubing leaked at a Swagelok fitting

Penex stabilizer overhead contains significant

chlorides boot of overhead receiver had been
overlayed with Monel and drain piping upgraded to
Hastelloy C276 to combat corrosion

Leaking Swagelok fitting or threaded connection in

seal flush line allowed chlorides in butane/propane
reflux stream to concentrate on outside of tubing

0.020 in

Chloride SCC

example: crude preflash tower overhead line 304 SS thermowell

304 SS thermowell removed from

crude unit preflash tower overhead
line for inspection during turnaround
was found to be cracked

Chlorides came from condensing HCl

in overhead stream

Thermowell was upgraded to Monel

0.020 in

Chloride SCC

example: sat gas plant deethanizer reboiler 2205 duplex SS tubes

0.020 in

0.001 in

150 psi (10.3 bar) steam-heated sat gas

plant deethanizer reboiler CS tube bundle
that historically leaked after a year of
service was upgraded to 2205 duplex SS

After a 4 year run, inch diameter x 0.065

inch (1.65 mm) wall tubes were found to
be pitted and cracked

Chlorides in unit feed from either crude

unit overhead or catalytic reformer
overhead streams concentrated in the
190F (88C) shell-side stream
10

Chloride SCC

prevention/mitigation

Select resistant materials of construction

Use low chloride (< 50 ppm Cl-) water for washing, hydroblasting, and
hydrotesting and dry out thoroughly and quickly
Apply coatings to insulated SS equipment to prevent external cracking
Avoid designs that allow stagnant regions where chlorides can
concentrate
Assure good draining of low point drains on start-ups
Repair steam tracing leaks in a timely manner

11

Chloride SCC
references

API RP 571, Damage Mechanisms Affecting Fixed Equipment in the

Refining Industry, Section 4.5.1
API RP 581, Risk-Based Inspection Technology, Part 2, Section 13

12

Caustic SCC

description of damage and affected materials

Description of damage
surface-initiated cracks, sometimes described as a spider web of
small cracks
usually little or no signs of other corrosion
fracture surfaces show little or no deformation
cracks typically run in base metal parallel to non-PWHTed welds
metallography of cracks in CS reveals a network of very fine, oxidefilled cracks
cracks in SS are typically transgranular and difficult to distinguish
from chloride SCC
Affected materials
carbon steel, low alloy steels, and 3xx series SS
Nickel alloys resistant but not immune to cracking

13

Caustic SCC
critical factors

Also known as caustic

embrittlement, both NaOH (caustic
soda) and KOH (caustic potash)
solutions should be treated the same

Increasing concentration and

increasing temperature increase the
likelihood and severity of cracking

Low caustic levels can become

concentrated by wet/dry cycles and
during steamout

Stresses approaching the yield stress

are believed to be required for
cracking PWHT of CS welds is
effective for preventing cracking

14

Caustic SCC
critical factors

Caustic SCC of 3xx series stainless

steels occurs at temperatures above
240F (115C)

Ni alloys (Monel 400, Inconel 600) are

highly resistant to caustic SCC and
are often used for heating coils in
caustic storage tanks

15

Caustic SCC

affected units or equipment

Piping and equipment that handle fresh and spent caustic

H2S and mercaptan removal equipment that uses caustic
neutralization equipment in HF and sulfuric acid alkylation units
caustic is sometimes injected into crude unit feed for overhead chloride
control
boiler feedwater and steam equipment, particularly if subjected to
alternating wet and dry cycles

16

Caustic SCC

example: 5# steam reboiler

A leak was found in the non-PWHTed carbon

steel channel of a reboiler that used 5 psi (0.3
bar) steam

The 5 psi (0.3 bar) steam was produced by

injecting boiler feed water into 50 psi (3.4 bar)
steam just upstream of the channel

Caustic in the BFW was concentrated by

evaporation leading to caustic stress cracking
that initiated adjacent to the partition plate-tochannel weld

Condensate should be used instead of BFW to

attemperate steam
17

Caustic SCC

prevention/mitigation

PWHT/stress relieve carbon steel welds and tube u-bends at 1175 25F
(635 14C)
while caustic storage tanks are not typically stress-relieved, the plate
containing the nozzles where heating coils enter the tank should be
PWHTed

Avoid steam-out of non-PWHTed carbon steel piping and equipment in

caustic service water washing is preferred
Use electric heat tracing in place of steam heat tracing. When steam
tracing is used, install with standoffs to prevent the tubing from directly
contacting the piping/equipment
Use Ni alloys such as Monel 400 or Inconel 600 for heating coils
Do not use boiler feed water to attemperate steam use only
condensate

18

Caustic SCC
references

API RP 571, Damage Mechanisms Affecting Fixed Equipment in the

Refining Industry, Section 4.5.3
NACE SP0403, Avoiding Caustic Stress Corrosion Cracking of Carbon
Steel Refinery Equipment and Piping

19

Amine SCC

description of damage/affected materials

Description of damage
surface-breaking cracks that initiate primarily in the HAZ of nonPWHTed carbon steel welds, but may also initiate in the weld metal
or highly stressed base metal
cracks are typically parallel to the weld and there may be parallel
cracks
cracks in the weld metal may be either longitudinal or transverse to
the weld
at set-on nozzles, cracks usually fan out radially from the bore

at set-in nozzles, cracks are usually parallel to the weld

cracks may be on the process side of external attachment welds
cracking is typically intergranular, branched, and oxide-filled
Affected materials
carbon and low alloy steels

20

Amine SCC
critical factors

Cracking is usually associated with residual stresses from welding,

forming or fabrication that have not been removed by PWHT
Cracking is more likely in MEA, DIPA and DEA services, but occurs in
other amines as well
Service temperature for which API RP 945 recommends PWHT are as
follows:
MEA, DIPA

all temperatures

DEA

140F (60C)

MDEA

180F (82C)

all other amines

190F (88C)

Need for PWHT should also consider effects of heat tracing and steamout on metal temperature.
Note that ETP GP36-12 requires PWHT for all amine services regardless
of operating temperature.

21

Amine SCC

critical factors and affected units or equipment

Amine SCC is most often associated with lean amine services

cracking in rich amine services is usually caused by wet H2S problems
Amine concentration does not appear to have a significant effect on
cracking

Affected units or equipment

Non-PWHTed carbon steel piping and equipment in lean amine
service including contactors, absorbers, strippers, regenerators and
heat exchangers, as well as equipment subject to amine carryover

22

Amine SCC

prevention/mitigation

PWHT all carbon steel welds in piping and equipment per GP 36-12,
taking into account the effect of heat tracing and steam-out
Water wash non-PWHTed CS piping and equipment prior to welding,
heat treatment, or steam-out
Use solid SS or clad/overlay carbon steel with SS

23

Amine SCC
references

API RP 571, Damage Mechanisms Affecting Fixed Equipment in the

Refining Industry, Section 5.1.2.2
API RP 945, Avoiding Environmental Cracking in Amine Units
NACE SP0472, Methods and Controls to Prevent In-Service
Environmental Cracking of Carbon Steel Weldments in Corrosive
Petroleum Refining Environments

24

Polythionic acid SCC

description of damage and affected materials

Description of damage
surface-initiated cracks typically in a network appearing to outline
grains on the surface

cracking usually occurs during shutdowns when sensitized SS is

exposed to air and moisture
cracking normally found either during the shutdown, during the
following startup, or soon after startup
usually little or no signs of other corrosion
fracture surfaces show little or no deformation
usually adjacent to welds or high stress areas
cracking can propagate rapidly through the wall thickness in a
matter of minutes or hours

Affected materials
3xx SS alloys
Inconel 600
Incoloy 800/800H/800HT
25

Polythionic acid SCC

critical factors

Material must be sensitized

regular and H grades of stainless steel can become sensitized
from the heat of welding
L grades and stabilized (321/347) stainless steels can be welded
without sensitizing

operation above 700F (370C) requires use of a stabilized

(321/347/347H) stainless steel
Environment
sulfide scale formed on metal surface while in service reacts with
oxygen and moisture during a shutdown to create polythionic acids
(H2SxOy where x ranges from 1 to 5 and y ranges from <1 to 6)
Stress
cracking is usually associated with residual stresses and sensitized
HAZ of welds

26

Polythionic acid SCC

affected units or equipment

Hydroprocessing unit heater tubes, feed/effluent piping, heat

exchangers, and bellows
FCC reactor and regenerator air rings, plenums, catalyst lines, cyclones,
and expansion joints
cracking in regenerators is more prevalent in units that operate with
a partial burn additional oxygen of full burn promotes formation of
oxide scales instead of sulfide scales
Crude and coker unit piping
few instances of cracking have been reported, it is believed heavy oil
films on equipment may provide protection

27

Polythionic acid SCC

example: diesel hydrotreater 304 SS effluent piping

inside surface of pipe

Transverse cracks were found in the

weld HAZ of a 304 SS bypass line
around a diesel hydrotreater reactor
effluent/recycle gas exchanger

The 304 SS was sensitized during

welding and the HAZ cracked when
polythionic acids formed during a
turnaround

0.010 in

inside surface of pipe

28

Polythionic acid SCC

example: Carson FCC regenerator 304H SS flue gas line

Carson FCC regenerator catalyst fines

removed from the 3rd Stage Separator
pass through the 4th Stage Separator
prior to entering the CO boiler. There
is an 8, 304H SS bypass line around
the 4th Stage Separator.

When in service, the bypass line

operates at 1135F (610C) which will
rapidly sensitize 304H SS

A crack in the bypass line was

discovered while the unit was
operating

Analysis indicates the crack was due

to PASCC

29

Polythionic acid SCC

example: Cherry Point Incoloy 800 hydrocracker REAC

Carbon steel reactor effluent air

coolers in Cherry Points hydrocracker
were upgraded from carbon steel to
Incoloy 800 following a fire in the
1970s

After about 30 years in service, a

small leak was discovered in one of
the Incoloy 800 header boxes while
the unit was online

Analysis indicated the Incoloy was

sensitized in a very narrow band
adjacent to the weld during original
fabrication and the leak was due to
PASCC

30

Polythionic acid SCC

prevention/mitigation

Select alloys that resist sensitization

up to 700F (370C)
304 SS and 316 SS (only if not welded or heat-treated)
304L SS and 316L
up to 850F (455C)
321 SS (non-thermally stabilized base material/ preferred that
welds are thermally stabilized)
up to 900F (480C)

347 SS (non-thermally stabilized base material/ preferred that

welds are thermally stabilized)
up to 1000F (535C)
321 SS and 347 SS (thermally stabilized including welds)

over 1000F (535C)

347H SS (thermally stabilized including welds)
31

Polythionic acid SCC

prevention/mitigation

Prevent polythionic acids from forming during shutdowns

exclude oxygen and moisture from equipment by using a dry
nitrogen purge
prevent condensation of moisture by using dehumidified air
(dewpoint should be at least 40F (22C) below ambient temperature)

maintain heater firebox temperatures above the dewpoint

Establish an alkaline film on surfaces prior to air exposure to neutralize
polythionic acids as they form
wash surfaces with a 2 wt% soda ash (sodium carbonate, Na2CO3)
see NACE RP0170 for details
use soda ash solution for hydrotesting and pigging heater tubes
Soda ash wash only when sensitized materials are present

32

Polythionic acid SCC

references

API RP 571, Damage Mechanisms Affecting Fixed Equipment in the

Refining Industry, Section 5.1.2.1
NACE RP0170, Protection of Austenitic Stainless Steels and Other
Austenitic Alloys from Polythionic Acid Stress Corrosion Cracking
During Shutdown of Refinery Equipment

33

Check your understanding

We often have inspection programs for caustic and amine stress

corrosion cracking.
Why is it that our preferred practice is to specify materials and
fabrication requirements to avoid stress corrosion cracking rather than
rely on inspection?

What are the weaknesses of relying on inspection to prevent failures by

stress corrosion cracking?

34