Corrosion inhibitors used in Jacket Water System

Jacket Cooling water system

In order to maintain mechanical strength the components surrounding the combustion zone must be
cooled. The most convenient cooling medium is water, the use of which could lead to possible problems of
corrosion and scaling if not properly treated.
Within the jacket water system a number of corrosion cells are available but the two most
common and most damaging are due to dissimilar metals and differential aeration. In both types of cell
there exists an anode and a cathode, the metals which form part of the jacket system, and an electrolyte
which is the cooling water. The rate at which corrosion takes place is dependent upon the relative areas of
the cathode and the anode and the strength of the electrolyte. It is the anode that wastes away. orrosion
due to temperature differences is avoidable only by the use of suitable treatments. !issimilar metals"a
galvanic cell is set up where two different metals and a suitable li#uid are connected together in some
way. $ll metals may be placed in an electro"chemical series with the more noble at the top . Those metals
at the top are cathodic to those lower down. The relative positions between two metals in the table
determined the direction and strength of electrical current that flows between them and hence, the rate at
which the less noble will corrode
Galvanic Action
orrosion within cooling systems can occur if the coolant, i.e. water, has not been properly treated. The
corrosion can take the form of acid attack with resultant loss of metal from a large area of the exposed
surface, or by %xygen attack characterised by pitting. $ primary motive force for this corrosion is &alvanic
action
The Galvanic Series.
%r 'lectromotive series for metals
Cathode
Gold and Platinum
Titanium
Silver
Silver solder
Chromium-Nickel-Iron (Passive)
Chromium-Iron (Passive)
Stainless Steel (Passive)
Copper
Monel
70!0 Cupro-Nickel
"7-!! Nickel-Copper
#$dro%en
lead
Tin
&-' Tin lead Solder
(ron)es
(rasses
Nickel
Stainless-Steel '*-* (+ctive)
Stainless Steel '*-*-! (+ctive)
Chromium Iron (+ctive)
Chromium-Nickel-Iron (+ctive)
Cadmium
Iron
Steel
Cast Iron
Chromium
,inc
+luminium
+luminium +llo$s
Ma%nesium
Anode
The metals closer to the anodic end of the list corrode with preference to the metals towards
the cathode end.
$ galvanic cell can occur within an apparently (omogeneous material due to several processes
on of which is differential aeration where one area is exposed to more oxygen than another. The area with
less oxygen becomes anodic and will corrode.
Galvanic action within metal
Galvanic action due to temperature gradient
This situation can exist in cooling water systems with complex layout of heat exchangers and
passage ways within the diesel engine. )ystems containing readily corrodible metals such as zinc, tin and
lead alloys can complicate and intensify problems by causing deposit formations.
Dierential Aeration
"Where only a single metal exists within a system corrosion can still take place if the oxygen content of
the electrolyte is not homogenous. )uch a situation can occur readily in a jacket water system as regions
of stagnant flow soon have the oxygen level reduced by the oxidation of local metal. The metal adjacent
to water with reduced levels of oxygen become anodic to metals with higher oxygen content electrolyte in
contact with it.. &enerally, the anodic metal is small in comparison the cathode i.e. the area of stagnant
flow is small compared to the area of normal flow of electrolyte, and high rates of corrosion can exist. %ne
clear case of this is the generation of deep pits below rust scabs.
Solutions
Water treatment
To remove the risk of corrosion it is necessary to isolate the metal surface form the electrolyte. %ne
method would be by painting, but this is impractical for engine cooling water passages. $ better solution
would be a system which not only searched out bare metal coating it with a protective barrier, but also
repaired any damage to the barrier.
for corrosion to occur four conditions must be met;
There must be an Anode
There must be a cathode
An electrolyte must be present
An electron pathway should exits
Corrosion !nhibitors
Corosion inhibitors are classified on how they affect the corrosion cell and are placed into three
catagories;
Anodic Inhibitors
Cathodic Inhibitors
Combination inhibitors/organic inhibitors
Common Corrosion !nhibitors
Principally Anodic Inhibitors
Chromate
Nitrite
Orthophosphtae
icarbonate
!ilicate
"olybdate
Principally Cathodic Inhibitors
Carbonate
Polyphosphate
Phosphonates
#inc
oth Anodic and Cathodic Inhibitors
!oluble Oils
"ercaptoben$othia$ole %"T&
en$otria$ole %#T&
Tolytria$ole %TT#&
Anodic !nhibitors
Nitrite %NO'
(
&" These are the most commonly used form of treatment and operate by oxidising mild steel
surfaces with a thin, tenacious layer of corrosion product *magnetite +e,%-.. /elatively high volumes of
treatment chemical are re#uired so this method is only viable on closed systems
)odium 0itrite" *sometimes with 1orate added."effective with low dosage, concentration non"critical. It is
non toxic, compatible with anti freezes and closed system cooling materials. It does not polymerise or
breakdown. (owever protection for non"ferrous materials is low. $n organic inhibitor is thus re#uired.
$lthough will not cause skin disease it will harm eyes and skin. $pproved for use with domestic fresh
water systems.
)odium 0itrite is a Passi)ator, a passivator will act chemically to produce an insulating layer
on the metal surface. Whenever corrosion takes place the corrosion products including bubbles of gas, are
released from the metal surfaces. 2assivating chemicals act on the corrosion products preventing release
from the metal surface and thus stifling further corrosion. If the insulating layer becomes damaged,
corrosion begins a gain and the passivator acts on the new products to repair the layer.
Chromate*s"the first passivator product was )odium hromate which was an excellent inhibitor.
Inexpensive, effective and concentration easily tested. orrosion may increase by incorrectly dosing,
dangerous to handle, poisonous and can cause skin disease. 0ot allowed where domestic water production
is in use *3acket water heated evaporators.. 4nfortunately it was also highly toxic, a severe pollutant and
staining agent, was imcompatible with antifreeezes, nd will attack zinc and soft solder slightly. !ue to its
toxicity is sometimes used as a biocide in such places as brine in large /eefer plants.
!ilicates" react with dissolved metal ions at the anode. The resultant ion5silicate complex forms a gel that
deposits on anodic sites. This gel forms a thin, adherent layer that is relaitvely unaffected by p( in
comparsion to other inhibitors. The inhibiting properties increase with temperature and p(, normal p(
levels are 6.7 to 89.7.
are should be taken with the use of silicates, which are often used for the protection of
systesm containing alumiinium. In the event of boiling increased concnetrations and lead to aggressive
corrosion due to the high p(.
Orthophosphate +orms an insoluble complex with dissolved ferric ions that deposit at the anodic site. It is
more adherent and less p( sensitive than other anodic inhibitors. The film forms in p( of :.7 to ;.9.
!osage is typically 89ppm in neutral water
Cathodic !nhibitors
Polyphosphate" +orms complexes with alcium, <inc and other divalent ions, this creates positively
charged colloidal particles. These will migrate to the cathodic site and precipitate to form a corrosion
inhibiting film. The prescence of calcium is re#uired at a typical minimum concentration of 79ppm.
'xtreme variations in p( can upset the film and a reversion to orthophosphate will occur with time and
temperature.
2ositively charged zinc ions migrate to the cathodic site and react with the free hydroxyl ions to form a
zinc hydroxide stable film at p( ;.- to =.>. If the water is too acidic the film will dissolve and not reform.
If it is too alkaline the zinc hydroxide will precipitate in bulk and not at the cathodic site.
PhosphonatesInitially introduced as scale inhibitors to replace polyphosphates, they exhibit absorbtion at
the metal surface especially in alkaline hard water. &enerally used with other inhibitor types
"oth Anodic and Cathodic !nhibitors
en$otria$ole and Tria$ole )pecific corrosion inhibitor for copper. They break the electrochemical cirsuit by
absorbing into the copper surface.
They are generally added to standard treatments.
!ollble and dispersible oils+2etroleum industry recognised that emulsifying cutting oils *erroneously called
soluble oils. were able to reduce corrosion on metals by coating the surface. There were disadvantages
though, if the coating became too thick then it could retard the heat transfer rate. $dherent deposits form
as organic constituents polymerise or form break down products which can accumulate and disrupt flow.
?$0"1@W recommend it not to be used.
It is effective in low dosages, safe to handle and safe with domestic water production.
'ffectiveness is reduced by contamination with carbon, rust, scale etc. !ifficult to check concentration,
overdosing can lead to overheating of parts
%ils are classed as a barrier layer type inhibitor. The surfaces being coated in a thin layer of oil.
#odern treatment
0itrite"1orate treatment is most effective with a high #uality water base. This treatment has no scale
prevention properties and its effectiveness is reduced by high #uantities of dissolved solids.
$ modern treatment will be a 0itrite "1orate base, with a complex blend of organic and
inorganic scale and corrosion inhibitors plus surfactants, alkali adjusters, dispersants and foam
suppressers. $ high #uality water supply is still strongly recommended.
The $se o Sacriicial Anodes
"'lectrolytic protection for the whole system by the use of sacrificial anodes is impractical. 2arameters
such as water temperature, relative surface area of anode and cathode, activity of metals in system and
relative positions in galvanic series come into play. $nodic protectioon has become out of favour for
cooling water systems as it can lead to local attack, causes deposits leading to flow disturbance and it has
no scale protection
%reparation or cooling water treatment
"$ll anodes should be removed and the system inspected. 0o galvanised piping is to be used *old piping
can be assumed to have had the &alvanising removed.. (igh #uality water should be used and chemicals
measured and added as re#uired. $ history log should be kept
#icrobiological &ouling
4nder certain conditions bacteria found in cooling water systesm can adapt to feed on the nitrite
treatment.This can lead to rapid growth, formation of bio"films, fouling and blocakages.
Typical evidence is a loss of nitrite reserve but a stable or rising conductivity level as the nitrate formed
still contributes to the conductivity,
2roblems of this sort are rare due to the ellevated temerpatures and p( levels. )(ould it occur treatment
with a suitable biocide is re#uired.