CREVICE [1]

Crevice is a form of a localised physical deterioration of a metal surface that

takes place at environments distinctly different from the bulk environment, such
as; gasket joints, shielding by corrosion products and fouling deposits, stagnant
regions and complex geometric designs with sharp edges areas.

This usually starts with an infiltration of a corrosive substance into a crack or

small opening such as clearances between rolled tubes and tube sheets.

A crevice shields part of the surface and thereby enhances the formation of
differential aeration and chloride concentration cells, thus the crevice serves as a
ready-made initiation site for localised corrosion. The attack occurs because part
of the metal surface is in a shielded o restricted environment, compared to the
rest of the metal which is exposed to an electrolyte (seawater).

Initially anodic and cathodic processes occur all over the surface of the metal.

As oxygen is used up near the surface more oxygen diffuses in from the
surrounding electrolyte. The crevice then becomes an anode and the net charge
in the crevices becomes positive. This set up a potential difference and negative
ions from solution flow into the crevice to try and balance the charge. These ions
are usually Cl-. The chloride ions encourage corrosion and also form complexes
with the metal ions that react with water to produce acid. The acid combined with
[1]
chloride ions encourages further attack on the metal.
[2]
Corrosion mechanism in Ni alloys

Ni-Cr-Mo alloys do exhibit both pitting and crevice corrosion due to they are
subject to film breakdown and transpassive dissolution however, because as
crevice occurs at milder conditions (lower potentials, lower temperatures,
and/lower chloride concentration), it is the limiting factor.

The criterion adopted to determine the electrochemical conditions for the

propagation of crevice in Ni alloys, is that the corrosion potential E CORR must
exceed the re-passivation potential for a creviced sample. (E RCREV).

ECORR - ERCREV > 0.

This is itself a conservative indicator of crevice initiation, since E RCREV is actually

the potential at which a propagating crevice ceases to grow. Increasing
temperature leads to a decrease in ERCREV., chloride promotes film breakdown.

Effect of Sodium Chloride on crevice [3]

As the equipment is handling sodium chloride concentrate water (seawater),

initiation of crevice is attributed to the combination of depletion of oxygen and the
accumulation of chloride and hydrogen ions in the crevice. As the oxygen in the
crevice is depleted ferrous ions rom the corrosion reaction are accumulated, and
negatively charged chloride ions must enter the crevice to maintain electrical
neutrality. This phenomenon accelerates the following hydrolysis, which it will
finally lead to formation of rust, 2 Fe2O3H20 .

Fe++(Cl-)2 + H20 Fe(OH)2 +2H+ +2Cl-

4Fe(OH)2 + O2 2 Fe2O3H20 + 2H20

Effect of mechanical expansion

As part of the construction process of the heat exchanger, mechanical expansion
of the tubes against the tubesheet has been achieved using roller expanders.
This deformation causes a permanent change in shape, a plastic deformation
causing an increasing radial force exerted at the contact point between the rolls
and the tube. Either axial or torsional stresses can be created depending on the
method used. [4]

Moreover, mechanical expansion may cause tube-end fatigue; depending upon

the frequency and amplitude of stresses the rollers apply. This rolling process
reduces the tube wall by; either stretching the tube radially or by imposing high
unit rolling forces that cause the tube to extrude axially.

Because mechanical rolling pushes the tube material out the rear of the
tubesheet, a very noticeable rear crevice is often created, these spaces are
active sites for deposition and crevice attack. Pressure conditions, over rolling or
axial scratches in the hole or tube material could have been responsible for
reducing joint strength and increase tendency to leak.

All this stress concentration at this location within the construction where the joint
of stress and corrosive medium cause material deterioration, increased
temperature and rack geometry may accelerate corrosion. This is also supported
by the results from the ASTM G48-A Crevice Corrosion Testing provided, which
indicates that the standard tubes performed better than the over-expanded ones.

Effect of Temperature on Crevice [5]

According to ASTM G48 test, the higher alloy C22 have sufficient alloying to be
completely resistant to crevice attack up to temperature limit of 85 C in
aggressive environment and up to 103 C in very corrosive environment (the
green death solution: 11.9% H2SO4 + 1.3%HCl + 1% FeCl3 + 1% CuCl2 ). In this
case as where the tubes are in contact with two fluids of completely different
properties (seawater and condensing vapours), one of the severest environments
from the point of view of corrosion.

This could explain why C22 experience significantly attack in the bottom right
hand side of the heat exchanger where the gas stream enters in at 160 C,
clearly over its crevice critical temperature. In addition, as the material has been
subjected to this heating, intergranular attack (IGA) in service could have been a
factor that aided to set up the proper environment for crevices formation. This
phenomenon is called sensitization. Heating predisposes recrystallization, new
grains form, they can have fewer dislocations and the original properties of the
alloy can change including its resistance properties.

On the other hand, corrosion and pitting is a condition sometimes encountering

during shut down as it means periods when there is no fluid flow.

Recommendations

The best prevention of crevice corrosion is a design in which the stagnation

areas of the fluid flow and sharp corners are reduced to a minimum. Design
should be adjusted for complete drainage
Tube-to- tubesheet welding is preferred over the rolled variety to avoid the stress
created by the expansion process as the strength in this case is primarily
provided by the welding procedure. This leads to reduce the likelihood of the
crevice corrosion. However, all tube-to-tubesheet joints may leak to some degree.
[4]
As a general rule the smaller the clearance the better, from the expanding point
of view, hence constant inspection is needed.
Harmful surface deposit can be removed by cleaning. Filtration can eliminate
suspended solids that could otherwise settle out and form harmful crevice
conditions; agitation can be beneficial in this sense.
References:

[1] Jones D.A., Principles and prevention of Corrosion 359. Prentice Hall, United
States of America, 2nd Edition. 1996.

[2]https://www.nda.gov.uk/documents/biblio/upload/Review-of-the-corrosion-
performance-of-selected-metals-as-canister-materials-for-UK-spent-fuel-and-or-
HLW-Appendix-E-nickel-alloys.pdf

[3]Chang T., Lansing F., Review of Corrosion Causes and Corrosion Control in a
Technical Facility, TDA progress report, 1962.
[4]http://www.haskel.com/StaticFiles/MRContent/StaticFiles/Haskel/en/PDF;s/Tu
be%20Expansion%20Issues%20&%20Methods.pdf

[5] McCoy S., Shoemaker L., Corrosion Performance and Fabricability of the new
Generation of Highly Corrosion-Resistant Nickel-chromium-Molybdenum alloys,
Special Metals, USA