The Impact of Chlorides on

Cooling Water System

M t ll i d Pitti Metallurgies and Pitting
Alf P l Alfonso Palazzo
Feb 2009
Stainless Steel Stainless Steel
Stainless steel has provided good service in many applications. However,
f th i t d i i t t t th lti t f th use of the appropriate grade is important to the ultimate success of the
steel.
Corrosion should be an expected by-product of any steel use, including p y p y , g
stainless steel. The question is, how much corrosion is acceptable in the
intended application?
Corrosion is the deterioration of a metal or alloy as the result of exposure Corrosion is the deterioration of a metal or alloy as the result of exposure
to and reaction with its environment. It is an electrochemical process
The first equation is anodic and the rest are cathodic. Corrosion of
stainless steels is dependent almost entirely on chlorides,
sulphates and dissolved oxygen content. Chlorides also can be
adsorbed or chemisorbed in films on the metal surfaces (silicates, ( ,
aluminates, iron oxides and calcareous deposits).
The typical reactions are
Fe0 Fe2+ + 2e
2H+ + 2e H2O 2H+ + 2e H2O
2H+ + 1/2O2 + 2e H2O
H2O + 1/2O2 + 2e 2OH
Chl id i i Wh h hl id d 50 /L 304 i l Chloride pittingWhen the chlorides exceed 50 mg/L, 304 stainless
steel should be used instead of carbon steels.
Where the chlorides exceed 200 mg/L, 316L would be preferred. g , p
Manufacturers often recommend a chloride ceiling for Type 316L
of 500 mg/L. This level is below all brackish water sources.
Chl id i d d itti i th bl l d b t l Chloride induced pitting is another problem resolved by metal
selection. Inappropriate metal selection can lead to serious damage
to the pipe, as well as microbial colonization
The conditions that lead to pitting are moderately high temperatures,
high concentrations of chloride ions (from salt), other halides such
as fluorides bromides and iodides Acidic conditions (lowpH) also as fluorides, bromides and iodides. Acidic conditions (low pH) also
aid the growth of the pits, which are themselves acidic.
This acidity within the pit is the reason why pits can continue to grow
th h b i iti t d once they have been initiated.
PREN the Pitting Resistance Equivalent Number
The PREN number is a useful guide to the
tendency of certain stainless steels to
pit It should be used as a guide only & pit. It should be used as a guide only &
not as a totally predictive measure that will
totally guarantee pitting resistance in all
i t All th t h hi h
Typical values of PREN
are:-
circumstances. Alloys that have high
concentrations of nitrogen (N), chromium
(Cr) and Molybdenum (Mo) have been
are:
Grade.........PREN
430............16
444.............25
found to show good resistance to
pitting. The relative effect of these
elements in combination is given by:
444.............25
304.............19
304LN..........21
316.............26 g y
PREN = (%Cr) + (3.3x%Mo) + (16 x %N)
(note that some variants use 32 x %N )
316LN.........27.5
904L...........36
Zeron 100...41
High PREN numbers therefore mean
higher resistance to pitting corrosion.
SAF 2507.....42
Larson Skold Index Larson-Skold Index
The Larson-Skold index describes the corrosivity of water towards mild steel.
The inde is the ratio of eq i alents per million (epm) of s lphate (SO4) and chloride The index is the ratio of equivalents per million (epm) of sulphate (SO4) and chloride
(Cl) to the equivalents per million of alkalinity in the form bicarbonate plus carbonate
(HCO3 + CO3).
Larson-Skold index = (epm Cl + epm SO4)
(epm HCO3 + epm CO3)
It must be noted that the Larson-Skold relationship is based upon Great Lakes It must be noted that the Larson-Skold relationship is based upon Great Lakes
waters. Extrapolation to other waters, such as those of low alkalinity or extreme
alkalinity, goes beyond the range of the original data.
The index might be interpreted by the following guidelines: g p y gg
Larson-Skold Indication
<< 0.8 Chlorides and sulphate probably will not interfere with natural film formation.
>> 0.8 but << 1.2 Chlorides and sulphates may interfere with natural film formation. Higher than
desired
corrosion rates might be anticipated.
>> 1.2 The tendency towards high corrosion rates of a local type should be expected
as the index increases.
Crevice Corrosion Of Stainless Steels
Crevice corrosion is the second most common modem failure of
stainless steels with pitting corrosion being the most common stainless steels, with pitting corrosion being the most common.
Crevice corrosion occurs at locations where there is a small gap, or
crevice, between the stainless steel article and another item. This
second item can commonly be an insulator such as a gasket or a
rubber separator although it could be metallic. The actual geometry
of the small gap is critical for the onset of crevice corrosion. The gap g p g p
has to be just big enough to allow an aggressive liquid to penetrate
into the gap but not big enough to allow material to be flushed out of
the gap due to flowor confection in the fluid. the gap due to flow or confection in the fluid.
The mechanism of crevice corrosion is well-known, with the first
stage being the accumulation of aggressive ions (such as chloride
i ) i th d th l i f f th l ti ithi ions) in the gap and the exclusion of oxygen from the solution within
the gap. This results in a fixed anode forming in the crevice with the
material outside of the crevice becoming a fixed cathode.
Stress Corrosion Cracking Stress Corrosion Cracking
Prevention of SCC
1. Lowering the stress below the threshold value if one exists. This may be
d b li i th f id l t thi k i th ti done by annealing in the case of residual stresses, thickening the section, or
reducing the load. Plain carbon steels may be stress-relief annealed at 590 to
650C, and the austenitic stainless steels are frequently stress-relieved at
t t i f 820 t 930C temperatures ranging from 820 to 930C.
2. Eliminating the critical environmental species by, for example, de-
gasification, demineralization, or distillation.
3. Changing the alloy is one possible recourse if neither the environment nor 3 C a g g t e a oy s o e poss be ecou se et e t e e o e t o
stress can be changed. For example, it is common practice to use Inconel (raising
the nickel content) when type 304 stainless steel is not satisfactory. Although
carbon steel is less resistant to general corrosion, it is more resistant to stress- g
corrosion cracking than are the stainless steels. Thus, under conditions which tend
to produce stress-corrosion cracking, carbon steels are often found to be more
satisfactory than the stainless steels. For example, heat exchangers used in
9
contact with seawater or brackish waters are often constructed of ordinary
mild steel.
4. Applying cathodic protection to the structure with an external power supply or pp y g p p ppy
consumable anodes. Cathodic protection should only be used to protect
installations where it is positively known that stress-corrosion cracking is the cause
of fracture, since hydrogen embrittlement effects are accelerated by impressed
cathodic currents cathodic currents.
5. Adding inhibitors to the system if feasible. Phosphates and other inorganic
and organic corrosion inhibitors have been used successfully to reduce and organic corrosion inhibitors have been used successfully to reduce
stress-corrosion cracking effects in mildly corrosive media. As in all inhibitor
applications, sufficient inhibitor should be added to prevent the possibility of
localized corrosion and pitting. p g
6. Coatings are sometimes used, and they depend on keeping the environment
away from the metal - for example, coating vessels and pipes that are covered with y p g pp
insulation. In general, however, this procedure may be risky for bare metal.
7. Shot-peening (also known as shot-blasting) produces residual compressive
stresses in the surface of the metal. Very substantial improvement in resistance to
stress corrosion found as a result of peening with glass beads. Type 410 stainless
was exposed to 3% NaCl at room temperature; type 304 to 42% MgCI2 at 150C;
and aluminumalloy 7075 T6 to a water solution of K2Cr2O7 CrO3 NaCl at room
10
and aluminum alloy 7075-T6 to a water solution of K2Cr2O7-CrO3-NaCl at room
temperature.
Aluminium Aluminium
Aluminium alloys are widely used structural materials in
the industry because of their high strength-to-weight ratio
and good fracture toughness and good fracture toughness.
Their resistance to corrosion depends upon the rapidly
formed stable oxide film formed stable oxide film.
However, in the presence of aggressive anions, such as
halide, which can destabilize the passive film over the a de, c ca des ab e e pass e o e e
matrix, aluminium alloys are subject to localized
corrosion.
Aluminiumcontin Aluminium contin.
Al i i d i i i i hl id i l l Aluminium tends to pit in waters containing chlorides, particularly at
crevices or at stagnant areas where passivity breaks down through
the action of differential aeration cells.
The mechanism is analogous to that for stainless steel.
Copper and its alloys Copper and its alloys
C i f i i ll i h b f Corrosion of copper-containing alloys in the absence of
complicating, aggressive variables decreases as the system pH
increases. Variables affecting copper corrosion and its alloys
are ammonia and ammonia ions, hydrogen sulphide and other
sulphur compounds, and aerated acidic waters.
Waters high in oxygen and carbon dioxide and low in calcium Waters high in oxygen and carbon dioxide and low in calcium
and manganese hardness, waters high in chlorides and
hypochlorite ion and waters high in bicarbonate alkalinity also
affect copper corrosion affect copper corrosion.
The corrosion resistance of copper metal in cooling water
systems depends on the stability of the protective oxide film.
Any contaminant that interferes with the protective oxide film
formation or stability will increase copper attack.