Caustic Stress Corrosion Cracking

Caustic SSC 1
Description of Damage
Caustic Stress Corrosion Cracking

• Caustic SCC is characterized by surface-initiated cracks that occur in piping
and equipment exposed to caustic (alkaline hydroxide solutions) at elevated
temperature, primarily adjacent to non-PWHT’d welds.
• It is a form of ASCC. The temperature above which caustic SCC occurs
depends on the concentration of the caustic solution.
Affected Materials
• CS, low-alloy steels, and 300 series SS are susceptible.

• Duplex SS are also susceptible but have shown improved resistance
compared to the 300 series SS.
• Nickel-based alloys are more resistant.
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Critical Factors
Caustic SSC 2
A) Susceptibility to caustic SCC in (NaOH) and (KOH) solutions is a function of caustic

strength, metal temperature, and stress level.
B) Increasing caustic concentration and increasing T increase the likelihood and rate of SSC.
• Conditions likely to result in cracking have been established through plant experience
and are presented in Figure (1)
C) Cracking can occur at low caustic levels if a concentrating mechanism is present.
In such cases, caustic concentrations of 50 ppm to 100 ppm are sufficient to cause
cracking.
D) Residual stresses from welding (in non-stress-relieved welds) or from cold working (such
as bending and forming) will cause cracking.
• Applied stresses, e.g. from pressure or mechanical loading, can also cause caustic SCC,
but this is uncommon since applied stresses are normally low relative to the yield point
and are lower than residual stresses from welding or forming
Caustic SSC 3
Fig (1) Recommended operating limits for carbon steel in caustic

service
Caustic SSC 4
Critical Factors
E) Thermal stress relief (PWHT) is effective in preventing caustic SCC.

F) Crack propagation rates increase dramatically with temperature, and
cracks can grow through wall in a matter of hours during temperature
excursions, especially in concentrated caustic or if conditions promote
caustic concentration.
• Concentration can occur as the result of
(1) alternating wet and dry conditions, (2) localized hot spots, or
(3) high-temperature steam out.
G) Special care must be taken with
(1) Steam tracing or heat tracing design (2) Steam out of non-PWHT’d
piping and equipment.
H) Contaminants in the caustic solution, especially sulfides, regardless of
concentration, will increase the likelihood of SCC in non-PWHT’d carbon
steel, including in the lower temperature area (area “A”) in Fig (1)
Caustic SSC 5
Affected Units or Equipment
A) Caustic SCC can occur in non-stress-relieved piping and

equipment that handles caustic,
(1) H2S and mercaptan removal units,
(2) Equipment that uses caustic for neutralization in sulfuric acid
alkylation units and HF alkylation units.
(3) Caustic is sometimes injected into the feed to the crude tower
for chloride control.
B) Improperly heat-traced piping or equipment as well as heating
coils and other heat transfer equipment.
C) Result of steam cleaning after being in caustic service.

Caustic SSC 6
Affected Units or Equipment

D) Traces of caustic can become concentrated in BFW and can

result in caustic SCC of boiler tubes that alternate between wet and
dry conditions due to overfiring.
• It can also occur in superheaters due to steam drum carryover.
E) In boilers at rolled tube joints due to caustic concentrating
between the tube and tube-sheet. Fig (4)
F) The result of un-intended carryover of caustic into equipment not
Fig (4) designed to handle hot caustic (e.g. not stress relieved), such as
steam condensate piping or process equipment downstream of a
caustic treating section of a process unit

Caustic SSC 7
Appearance or Morphology of Damage

A) Caustic SCC typically propagates parallel to the weld in adjacent
base metal, i.e. in the zone of highest welding residual stress but
can also occur in the weld deposit or HAZ and can be transverse to
the weld.
B) The pattern of cracking observed on the steel surface is
sometimes described as a spider web of small cracks that often
initiate at or interconnect with weld-related flaws that serve as
local stress risers.
C) Cracks can be confirmed through metallographic examination.
Cracks are typically branched and predominantly intergranular.
Cracking that occurs in as-welded CS typically appears as a
network of very fine, oxide-filled cracks.
Caustic SSC 8
Appearance or Morphology of Damage

D) Cracking in 300 series SS is most often transgranular

but can be intergranular even in non-sensitized material.
When trans-granular, it can be difficult to distinguish from
Cl− SCC.
• Caustic SCC should exhibit a black magnetite layer on
the crack surface, whereas Cl− SCC should not
produce that type of oxide scale.
E) Similarly, caustic SCC of nickel-based alloys has been
observed as either intergranular (Fig. 9) or trans-granular
(Fig.10)

Appearance or Morphology of Damage Caustic SSC 9
Fig (9) Intergranular caustic SCC in an expansion joint

Fig (10) Trans-granular caustic SCC in Alloy 825
bellows constructed of Alloy 625 in a 400 psig steam
superheater
Caustic SSC 10

Prevention / Mitigation
A) A heat treatment at 1150 °F (620 °C) minimum with a

minimum holding time of 1 hr is an effective for CS .
(1) In contaminated caustic solutions, stress relief may be
needed to prevent cracking of CS even at low, otherwise “safe”
temperatures (area “A” in Figure 1).
B) 300 series SS offer little advantage in resistance to cracking
over carbon steel.

Prevention / Mitigation
Caustic SSC 11
C) Nickel-based alloys are more resistant to cracking and may be required at higher T
and/or caustic concentrations.
• However, caustic SCC of these alloys has been observed at high T that promote the
formation of molten caustic in the absence of free water [604 °F (318 °C), at
atmospheric pressure].
• This damage has sometimes been referred to as molten caustic cracking.
D) Steam out of non-PWHT’d CS piping and equipment should be avoided. Where
necessary,
(1) equipment should be water washed before steaming out,
(2) only low-pressure steam should be used for short periods of time to minimize
exposure.
E) Proper design and operation of the injection system is required to ensure that caustic
is properly dispersed before entering the high-temperature crude preheat system.
Prevention / Mitigation Caustic SSC 12
f) Ensure all soda ash (sodium carbonate) solution that may have been used as a protective
measure against polythionic acid stress corrosion cracking (PTA SCC) in 300 series SS
Caustic Stress Corrosion Cracking equipment is drained prior to heating up as this soda ash can result in caustic SCC of 300 series
SS as well as Alloy 800 and Alloy 825 as the water is boiled away.
etched condition caustic cracking initiating on the ID of Cracking initiating on the inside surface
a CS socket weld in non-PWHT’d piping of a non-stress-relieved CS heat
in a suction drum downstream of a exchanger bend after 8 years in 15 % to
caustic scrubber. Unetched. 20 % caustic service at (60 °C to 115 °C)
Caustic SSC 1
3
Inspection and Monitoring

A) WFMT, ACFM, and ECT can be effective techniques to detect these surface-
breaking cracks.
• Proper surface preparation is necessary to ensure cracking is not masked by
blending or smearing metal into the cracks.
• The method of surface preparation is dependent upon the specific technique.
B) (SWUT and PAUT) can be effective to detect and size cracks.
• These UT techniques can be used to periodically monitor crack growth.
C) PT or MT can be effective.
• PT may not be effective for finding tight cracks, because the cracks are oxide
filled.
D) RT may not be effective in detecting fine, tight cracks.
E) AET can be used for locating cracks and monitoring crack growth.
F) Severe cracking can at times be identified visually.
1
4

Caustic SSC 1
5
NACE – SP0403

Caustic concentration greater than 5 wt% in the aqueous phase can produce SCC in CS.6 The
majority of users do not require PWHT on CS if the caustic concentration is less than 2 wt%,
regardless of temperature, and some users use 5 wt% as their threshold, as shown in area “D”
of the Caustic Service Chart. Caustic SCC sometimes occurs in services with lower bulk fluid
concentrations, usually in areas where local concentration effects occur.
For these instances, caustic concentrations of 50 to 100 ppm in the bulk solution may cause
cracking.7 Possible ways to prevent local concentrating effects are by avoiding departure from
nucleate boiling (DNB)(2), keeping internal surfaces sufficiently free of caustic deposits, and
avoiding formation of waterlines in components receiving high heat flux.
Caustic SCC is known to occur over a wide range of temperatures in CS, from approximately
46 °C (115 °F) to boiling temperatures (depending on caustic concentration)
Alternative welding methods such as temper bead welding and controlled deposition welding
are not effective in mitigating caustic SCC. These methods do not sufficiently reduce residual
stresses, and therefore shall not be considered in lieu of thermal stress relief

NACE – SP0403 Caustic SSC 1
6
The weld is a vertical butt joint made using the (SMAW)

process in a small shop-fabricated aboveground storage vessel
(without PWHT).
The vessel was used to store industrial NaOH at 20%
concentration and a temperature of 35 to 46 °C (95 to 115 °F).
Cracking was believed to have occurred during a single
thermal excursion experienced during batch diluting of 50%
NaOH.
Fig. (1) shows typical caustic SCC originating from the weld
cap surface. In this case, none of the cracks had propagated
Caustic SCC in CS Weld Metal
deeper than the cap pass. Fig (2)
Fig (1)
Fig. (2) shows the cracking within the rectangle depicted in Fig.
(1). The cracking was tight, filled with oxide, and typically
followed the ferrite part in the weld metal.
7
Caustic SCC in CS Base Metal

8
Caustic SCC in an expansion joint bellows constructed of UNS S32100 operating in a steam environment

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Caustic SSC 1

• CS, low-alloy steels, and 300 series SS are susceptible.

API 571 – Preparation Course

A) Susceptibility to caustic SCC in (NaOH) and (KOH) solutions is a function of caustic