Journal of Materials Processing Technology 166 (2005) 256–267

Cathodic protection of cooling water systems and selection of

appropriate materials夽
I. Gurrappa∗
Defence Metallurgical Research Laboratory, Kanchanbagh P.O., Hyderabad-500058, India

Received 13 May 2002; received in revised form 6 January 2003; accepted 1 September 2004

Abstract

The current article focuses mainly the necessity, types of cathodic protection and anodes available apart from a brief review on sacrificial and
impressed current cathodic protection (ICCP) anodes. Further, the advantages and disadvantages of each are also discussed. The necessity of
designing of an effective cathodic protection system for cooling waters pipelines has been emphasized. In addition, the economics of cathodic
protection has been highlighted with an example. After installation of CP system, operation and maintenance part has also been mentioned.
Finally, the selection of suitable materials and design for various applications has been highlighted.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Cooling water systems; Cathodic protection; Appropriate materials

1. Introduction protection is the only solution and in fact an ideal technique

Cooling water systems are essential in order to enhance
the efficiency of equipment by elimination of heat from the
heat exchangers. A cost-effective treatment coupled with
high-performance is the requirement in the cooling water
systems. A treatment package taking care of only either
corrosion or fouling control or microbiological control is
not sufficient. The treatment should eliminate both corrosion
as well as microbiological settlement successfully, which in
turn enhances the efficiency of the equipment. For effective
prevention of corrosion and fouling in side cooling water
systems is the use of efficient inhibitors in association with
suitable non-oxidizing biocides. However, some cooling
water system pipelines are buried in the soil. Soil side corro-
sion is imminent for such cooling water pipelines. Inhibitors
and another chemical treatments not going to work here
or application of anti-corrosive coatings on the surface of
pipelines alone also do not protect the systems well. Cathodic
夽 Presented in the All India Convention on “Cooling Water Treatment”
7–8th December 2001, Hyderabad-500058, India.
∗ Tel.: +91 40 4586515; fax: +91 40 4340683.
E-mail address: igpl@rediffmail.com.
for the protection of cooling water systems buried in the
soil.
Cathodic protection is more reliable, effective and eco-
nomic method for protection of a variety of pipelines,
tanks, marine structures including ships hulls and submarines
against corrosion. Cathodic protection works primarily by
depressing the natural corrosion potential of the structure to
be protected to a value where it does not corrode. Cathodic
protection can be obtained either by using sacrificial anodes
or by using impressed current cathodic protection (ICCP)
system. On the basis of experience, it has been established
that the corrosion of structural steel stops when its poten-
tial is −800 mV against silver/silver chloride or +250 mV
against zinc reference electrode or −850 mV against cop-
per/copper sulphate electrode. This potential is the most
significant measurement with respect to corrosion control.
Table 1 provides the potential of structural steel under differ-
ent conditions (overprotection potential, optimum potential
and corroding potential) with respect to three different ref-
erence electrodes which are normally in use for monitoring
the effectiveness of cathodic protection or to find out the
status of the structural steel in a given environment. For mea-
surement of soil to pipe potentials, Cu/CuSO4 electrode is

0924-0136/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmatprotec.2004.09.074
 I. Gurrappa / Journal of Materials Processing Technology 166 (2005) 256–267
Table 1
Corroding, optimum and overprotection w.r.t. Cu/CuSO4 , Ag/AgCl and Zn
Reference electrode Corroding potential
Copper/copper sulphate −0.65 or more
Silver/silver chloride −0.60 V or more
Zinc +0.45 V or higher
the most suitable while high-purity zinc and Ag/AgCl elec-
trodes are ideal in marine environment. It is necessary to
maintain the potential of the structures (pipes/tanks/hulls,
etc.) in protective range because underprotection or over-
protection are not useful. Underprotection cannot protect
the structure completely from corrosion while overprotec-
tion results in generating more hydrogen at the surface of the
structure (cathode) leading to either blistering or disbond-
ing of organic coatings applied on the steel surface or hy-
drogen embrittlement of the steel (loss of ductility through
absorption of hydrogen) or both. Apart from this, over-
protection causes wastage of electric power and increased
consumption of anodes. Therefore, it is normal practice to
design the cathodic protection system for a given structure
to maintain the protective potentials during the designing
period. The next section describes the basic principle of
protecting the structures by using sacrificial anodes, differ-
ent types of sacrificial anodes, merits and demerits of each
type.
2. Sacrificial anodes
The principle involved in the development of sacrificial
anodes for cathodic protection purpose is that galvanic cur-
rent flows when two dissimilar metals are electrically shorted
in the conducting environment. The noble metal gets pro-
tected with consuming the less noble metal. Aluminium, zinc
and magnesium alloys are more base materials than mild
steel/carbon steel, which are the structural materials for the
pipelines, offshore structures, ships, etc. and therefore pro-
duce galvanic current when coupled with the steel in the
seawater resulting in their sacrificial dissolution for protect-
ing the steel. Sacrificial anodes are often used in preference
to ICCP system when the current requirements are low and
in relatively low-resistivity environments. Capital investment
will generally be lower and it is often the most economical
method for short time protection.
The salient features of magnesium, zinc and aluminium
alloy anodes are discussed below.
2.1. Magnesium alloy anodes
They have a highly negative free corrosion potential
and thereby dissolve too vigorously in seawater. Therefore,
magnesium alloy anodes are restricted to the protection of
pipelines in the soil or the structures in estuarine waters
where the resistivity is high enough to limit the effective-
ness of zinc or aluminium alloy anodes. They have also
257
Optimum potential Overprotection potential
−0.85 to −1.0 V −1.05 or higher
−0.80 to −0.95 V −1.00 V or higher
+0.150 to 0.250 V +0.10 or less
used for protection of ships when they enter into high-
resistivity waters such as river water. The protection of
storage tanks containing fresh or brackish water is another
suitable application. These anodes are helpful in protecting
condenser boxes in cooling water systems. The current effi-
ciency, potential and life of magnesium alloy anodes are as
follows:
(i) The current efficiency is about 50% only.
(ii) Anodes have high driving voltage.
(iii) Areas in the vicinity of anodes get overprotected.
(iv) The life range is from 6 months to 20 months depending
on the system design.
2.2. Zinc alloy anodes
An important property of zinc alloy anodes is that the
capacity of the anode is virtually unaffected by the operat-
ing current density. Therefore, zinc alloy anodes are gener-
ally used for the protection of pipelines, where the effects
of burial together with a high-duty coating tend to give low-
anode current densities. Zinc anodes can be successfully used
for protection of structures in water or mud-resistivity up to
1000
cm. The driving voltage of zinc alloy anodes dimin-
ishes with increasing temperature such that they are virtually
ineffective at temperatures of above 60◦ C. Therefore, zinc
alloy anodes have limited application and cannot be used
for protection of structures where the temperature is high.
These anodes are suitable for protecting cooling water, gas
pipelines, storage tanks, etc. where the soil-resistivity is up
to 1000
cm. The following are the properties of zinc alloy
anodes:
(i) The efficiency is about 95%.
(ii) Anodes are too heavy and the structure gets appreciably
loaded with dead weight. However, there may not be a
problem with the pipelines buried in the soil.
(iii) High purity zinc (99.99%) is essential for reliable per-
formance.
2.3. Aluminium alloy anodes
These anodes became popular because of their superiority
over magnesium and zinc alloy anodes in respect of:
(a) low cost,
(b) long life,
(c) high energy capability and
(d) light weight.
258 I. Gurrappa / Journal of Materials Processing Technology 166 (2005) 256–267
These anodes are most ideal not only for the protection
of weight limited structures such as submarines and weapon
packages but also for all types of structures including off-
shore platforms and ships. The compositions used in com-
mercial scale generally contain 2–5% zinc and one of the
elements such as mercury, tin and indium as an activator.
Schrieber and Reding [1] developed an alloy (Al–Zn–Hg)
for the first time with mercury as an activator. This anode
had shown a current efficiency in seawater exceeding 90%
and current capacity of 2750 A h/kg. This alloy became pop-
ular soon after this investigation and marketed under the trade
name “Galvalum”. However, mercury is an environmentally
controversial element and some aluminium anode users pre-
fer not to use anodes containing mercury. This aspect made
Cathodic Protection Engineers find an alternative to mercury
and successfully developed some anodes with indium, bis-
muth, tin, etc. as activators. Based on the activating elements,
the aluminium alloy anodes can be subdivided into three
types:
(i) tin-activated aluminium alloy anodes,
(ii) bismuth-activated aluminium alloy anodes and
(iii) indium-activated aluminium alloy anodes.
2.3.1. Tin-activated aluminium alloy anodes
These anodes were developed by Keir et al. [2] and
have been in use for protection of ship’s hull. Its compo-
sition is (Al + 5% Zn + 0.12% Sn). The reported anode ef-
ficiency is 70%. The effectiveness of tin is attributed to
reduced ionic resistance of oxide films on Al–Sn alloys.
However, these anodes require controlled heat treatment
for their performance and better efficiency and as such are
not cost-effective. Gurrappa et al. [3] successfully avoided
the costly heat treatment process by the controlled addi-
tion of small amount of bismuth to (Al + 5% Zn + 0.25%
Sn). The effect of bismuth in improving the polarisation
behaviour of basic composition (Al + 5% Zn + 0.25% Sn)
was studied [3]. It was reported that bismuth helps in ex-
panding the aluminium matrix and thereby increases the
tin solubility in aluminium, which is the reason for en-
hanced anode capacity comparable to that of heat-treated
anodes. The results also show that anode capacities depend
on various compositions of tin-activated aluminium alloy an-
odes.
There are different views on the role of tin and assumed
that creation of additional cation vacancies by entering tin as
quadravalent Sn4+ is responsible for improving the cathodic
protection properties. However, no experimental evidence is
available on the subject. Recently, the mechanism involved
in increasing the anode efficiency before and after heat treat-
ment of tin-activated aluminium alloy anodes was explained
on the basis of surface free energy concept [4] which was
evaluated by determining the Young’s Modulus and atomic
spacing of the anode materials experimentally. It was clearly
shown that decrease in surface free energy with the addition
of tin to (Al + 5% Zn) and after the heat treatment is the prin-
cipal reason for increasing the cathodic protection properties
of these alloys.
2.3.2. Bismuth-activated aluminium alloy anodes
Murai et al. [5] reported that 0.005–1.0% bismuth addi-
tion is helpful in enhancing the anode efficiency of (Al + 5%
Zn) from 65 to 71%. Bismuth addition to tin-activated alu-
minium alloy anodes is advantageous in hot water boiler
applications [6]. But the details are not available since
this was patented. For seawater applications, suitable ad-
dition of bismuth was identified and the anode efficiency
of (Al + 5% Zn + 0.2% Bi) was improved to 83% by the
addition of 2% magnesium [7]. It was reported that ex-
pansion of aluminium lattice and grain refinement after
the addition of 2% magnesium are the responsible fac-
tors in increasing the efficiency. It was also shown that
(Al + 5% Zn + 0.2% Bi + 2% Mg) is superior to other ternary
aluminium alloys containing different percentages of bis-
muth.
2.3.3. Indium-activated aluminium alloy anodes
Sakano et al. [8] developed indium-activated aluminium
alloy anodes and their composition is (Al + 5% Zn + 0.03%
In). They exhibit anode efficiency of 80%. These anodes do
not require
(a) any heat treatment,
(b) no reported pollution problem,
(c) exhibits maximum efficiency and
(d) works satisfactorily in seawater mud in addition to ex-
cellent performance in seawater.
Once indium is dissolved, it is immediately reduced at
localised sites and thus promotes activation. It is impor-
tant to note that presence of chloride ions in solution is
essential for indium to activate aluminium [9–12]. The re-
duced indium ions produce a highly polarizing condition,
which promote chloride migration and adsorption, thereby
enhancing aluminium dissolution by forming complex chlo-
rides. Reboul et al. proposed a three-step mechanism for
the activation of aluminium by indium [10] and mercury
[13]. However, experimentally established mechanisms have
not been reported in the literature to the best of author’s
knowledge.
The anode efficiency was improved to 90% by the ad-
dition of 2% magnesium [14] to (Al + 5% Zn + 0.03% In).
Tamada and Tamura [15] have confirmed that magnesium
addition to (Al + 5% Zn + 0.03% In) is helpful in improv-
ing the cathodic protection properties. Homogenisation of
(Al + 5% Zn + 0.03% In) [16] and (Al + 5% Zn + 0.03%
In + 2% Mg) [17] exhibits improved anode performance. Ho-
mogenisation of (Al + 5% Zn + 0.03% In + 2% Mg) followed
by water quenching have improved Ecorr and corrosion
current compared to as cast and furnace cooled anodes
[18]. However, the major limitation of aluminium alloy
anodes is that these anodes work satisfactorily only in
high-conductivity environments. Therefore, for protection of
 I. Gurrappa / Journal of Materials Processing Technology 166 (2005) 256–267 259

cooling water systems, either Zn or Mg alloy anodes are more impressed on the pipes which act as cathode via inert an-
suitable. odes. The ICCP system consists of three essential compo-
nents, namely, (i) inert anodes (ii) reference electrodes and
2.3.3.1. Advantages of sacrificial anodes. (iii) auto-control/rectifier unit.

(1) They operate independent of electric supply. 3.1. Inert anodes

(2) They are relatively simple to install. Additional an-
odes can always be fitted if adequate protection is not Numerous materials can be used as inert anodes, but only
achieved. few materials satisfy all the parameters required for practical
(3) There is no electrical hazard to the divers. application in view of limitations imposed by electrochemical
(4) No control to be exercised. dissolution rate and/or mechanical durability or both [19].
(5) Incorrect fitting problem can be eliminated. The anodes which have been used and are in use for different
(6) Minimum maintenance costs applications are as follows:
(7) Installation costs are low.
(a) mild steel,
However, following are the limitations of sacrificial an- (b) ferrosilicon,
odes. (c) graphite,
(d) lead alloys,
2.3.3.2. Disadvantages. (e) magnetite and
(f) platinized titanium anodes.
(1) Periodic replacement is essential, as the life of anodes is
limited. Table 2 provides characteristics of various types of ICCP
(2) Current output cannot be regulated according to the de- anodes. It is clearly observed that each anode has unique
mand (pollution, paint damage, etc.). properties that influence the performance in a given environ-
(3) Not economically viable for protecting large and poorly ment and the performance varies from one environment to
coated pipelines. the other. It is worthwhile to emphasize here the properties
(4) Necessity of large number of anodes results in increase of inert anodes, which should posses for proper functioning
of frictional drag and weight. in different environments.

3.1.1. Desirable properties of inert anodes

3. Impressed current cathodic protection system (a) good electrical properties,
(b) low rate of consumption,
This is the most ideal and rugged system and has been (c) low-anode polarisation,
in use in most of the pipelines for protection including ship (d) good mechanical properties,
hulls and submarines all over the world. In this system, the (e) capable of forming different shapes and
protection current is drawn through the power supply and is (f) an attractive low cost.

Table 2
Comparative performance of different types of ICCP anodes in various environments
Anode Consumption Maximum Optimum Seawater Fresh water Soil Limitations
materials (kg/A Y) utilization current density
(%) (A/m2 )
Platinized 6–8.6 × 10−6 85a 32.4 400/1 ␮m 400/1 ␮m 81/1 ␮m Costly and the voltage should not
metals of Pt of Pt of Pt exceed 8 V
Lead base 0.09 67 – 200 – – Not suitable in fresh waters and soils
alloys
Mild steel 9–10 50 – No limit No limit 5 Consumption is very high
Ferrosilicon 0.25 50 – No limit 26b 11 Not suitable in high-chloride media
Si–Cr–Fe 0.25 50 – 26 26 11c Not suitable in low-resistivity soils
Graphite 0.1–1.0 66 – 11–30 8 8–11 Not suitable in wet soils and high
temperatures
Magnetite 0.005–0.08 40 – 77 – 30 Sintered magnetite anodes do not
work in pH <5 while as cast anodes
work successfully between pH 1 and
10, but fails rapidly in pH <1
a Consumption of platinum.
b Not recommended above 200 ppm Cl and temperature of +38 ◦ C.
c Maximum 5.5 A/m2 in deep ground beds.
260 I. Gurrappa / Journal of Materials Processing Technology 166 (2005) 256–267
An ideal inert anode is one, which can satisfy all the above
properties and thereby lasts long with satisfactory perfor-
mance. However, no single material can easily meet all the
requirements. Among the ICCP anodes mentioned above,
platinized titanium anodes became popular for the protec-
tion of pipelines and marine structures. A brief review on
these anodes has mentioned below.
3.1.2. Platinized titanium anodes
This type of anodes has very good cathodic protection
properties and they have been showing excellent performance
as evidenced from the reports of different pipelines and var-
ious classes of marine structures all over the world. Their
extensive use was restricted due to their high cost [20,21].
In view of this, a very thin film of platinum was deposited
through electrochemical route on titanium. Great care has to
be taken in design and installation of these anodes in such a
way that the working potential should not exceed 8 V, which
is the breakdown potential of titanium in chloride containing
environments. However, this problem can be solved by using
niobium, tantalum or ruthenium in place of titanium where
the working potential exceeds more than 8 V. The platinized
titanium anodes have been in use for cathodic protection of
oil production platforms, drilling rigs, ship hulls, pipelines,
jetties, seawater circulation systems, etc. In fact, most of the
pipelines and ships in the world are fitted with platinized
titanium anodes and their performance is excellent. The con-
sumption rate of platinum can be increased by 10-fold in fresh
waters i.e. where oxygen evolution is predominant.
Table 2 illustrated comparative performance of various
types of ICCP anodes in different environments. Recently, a
new type of anodes such as ceramic coated and conductive
rubber anodes have been developed and a brief on each is
given below.
3.1.2.1. Ceramic-coated anodes. Kumar and Armstrong
[22] developed ceramic-coated anodes for cathodic protec-
tion of lock mitre gates, tainter gates and elevated water tanks.
The potential surveys on the actual sites after installation of
ceramic-coated anodes have shown satisfactory performance.
These anodes are superior to graphite and silicon-iron an-
odes and the dissolution rate is less than 0.001 g/A Y. They
are prepared by depositing precious mixed-metal oxide films
of ruthenium oxide or iridium oxide combined with titanium
oxide on titanium substrate. Different shapes of these anodes
can be prepared and the configurations currently used are
flat-disc and rod-type ceramic coated anodes.
Flat-disc anodes consist of a precious metal oxide film de-
posited on a 5 in. diameter titanium disc substrate. They are
less susceptible to mechanical damage due to its flat surface
and introduction of polyurethane disc behind the substrate
material. These anodes have factory made electrical connec-
tions with a series of redundant waterproof seals designed to
eliminate problems with anode shorting or electrical connec-
tion.
Rod-type anodes are similar to the flat-disc anodes except
that the ceramic coating is deposited on a 4 ft long titanium
rod having male/female connectors to allow for a variety of
usable lengths. Since the consumption is very low, these an-
odes are lightweight and installation is easy. The advantages
of ceramic-coated anodes are as follows:
(1) The anodes have a lightweight design that allows easy
installation.
(2) Anodes can be installed underwater, eliminating the need
to wait for denaturing of the structure.
(3) Due to anode’s factory made connection, the problem of
electrical shorting to the structure can be virtually elim-
inated.
(4) The anodes resist damage from ice and floating debris.
3.1.2.2. Conductive rubber anodes. A method was devel-
oped by Kesser and Powers [23] using conductive rubber
anodes to cathodically protect steel reinforced concrete pil-
ing in marine environments. The potential data obtained after
installation of the conductive rubber system on a bridge indi-
cates that a conductive rubber system can be used to produce
uniform potential distribution. The results show that cathodic
potentials can be continuously maintained in both the splash
and in the submerged zone under all variable conditions.
The conductive rubber system is made from ethylene–
pylene–diene monomer (EPDM) containing 25% volume
acetylene black conductive carbon. The conductive rubber
is bathed and passed through an extruder to produce a sheet
1/4 by 5 in. wide in corrugations on one surface. The cor-
rugated face for the tidal waters to wet the concrete-rubber
surface during high-tide period. The volume activity of the
rubber is approximately 1.5
cm.
Among the ICCP anodes described above, only platinized
titanium anodes, conductive rubber and mixed metal oxide
anodes have been in use for protection of pipelines. The
platinized titanium anodes show superior performance com-
pared to other types of anodes developed till today. These
anodes operate at high-current densities and have long life.
In addition, these anodes can also be used in high-resistivity
waters effectively. For protection of the structures, the num-
bers of anodes have to be decided based on the exposed con-
ditions, the nature of coatings, etc.
3.2. Reference electrodes
The purpose of the reference electrodes is to measure and
monitor the pipeline condition through auto-control/rectifier
unit. A copper/copper sulphate electrode is generally used
and of course ideal for measuring the pipe-to-soil potentials
and the performance of the ICCP systems is adjudged by
potential survey. Silver/silver chloride seawater electrode is
an ideal non-polarizing reference electrode for seawater en-
vironment. An alternative is the use of high-purity zinc. The
number of reference electrodes has to be decided based on the
exposed conditions, type of coating applied, etc. The number
 I. Gurrappa / Journal of Materials Processing Technology 166 (2005) 256–267 261

and position of reference electrodes and inert anodes on the

underground pipelines is of utmost important in designing an
efficient ICCP system for effective protection of any structure
including the cooling water systems.

3.3. Auto-control/rectifier unit

This unit is useful to provide the required dc current to

the pipeline depending on the voltage signal of the reference
electrode. The capacity of the auto-control unit is another
important parameter in addition to the position of inert an-
odes and reference electrodes for designing an ideal system
for a particular type of structure and different diameters of
pipelines.

3.3.1. Advantages of ICCP system Fig. 1. Soil side corrosion at the coating failure region.
(i) Large driving potential.
(ii) Higher current output. nance problems as well as shut down time [24]. The cathodic
(iii) Flexibility of current output control. protection is not only acts as a supplementary measure but
(iv) Applicable in almost any resistivity soil environment. also provides a complete protection to all types of structures.
(v) Applicable for poorly coated pipelines. The severity of corrosion increases significantly in soil envi-
(vi) Protects larger and more expensive pipes. ronment if chloride ion concentration is more than 100 ppm,
sulphate content is more than 200 ppm, soil-resistivity is
3.3.2. Disadvantages less than 1000
cm, kind of soil is peat, mud or bog type
(i) Higher installation costs. and activity of sulphate reducing bacteria is present in the
(ii) Higher maintenance costs. soil.
(iii) Requires constant supervision to ensure the system is The design of cathodic protection system should be highly
operational. essential in order to ensure the integrity of cooling waters sys-
tems and thereby enhances the efficiency of the equipments
by elimination of failures. To design an effective cathodic
4. Cathodic protection of cooling water systems protection system, some important factors should be known.

The present day industries like refineries, chemical plants, 4.1. Important factors for cathodic protection system
fertilizers, petrochemical complexes and product distribution design
terminals have several kilometers of piping (different diame-
ters) depending on their capacity. These underground piping The cooling water piping cathodic protection system
is meant for cooling water, firewater, raw water condensate, design is a serious engineering activity, which is to be
process fluids, etc. All the piping lines are prone to pitting
corrosion in the soil, severity of which depends mostly on
the type and quality of coating and soil-resistivity of the
particular plant area (Figs. 1–6) [24]. Therefore, it is essen-
tial to combat soil corrosion effectively by the application
of efficient cathodic protection system in conjunction with
high-performance anti-corrosive coatings. The other protec-
tive measures are taken are the anti-corrosive coatings. Due to
the presence of holidays as well as defects (during handling
or installation) cannot provide complete protection. Further,
the application of anti-corrosive coatings is difficult task for
smaller diameter pipelines. Besides, cooling water systems
buried in the soil are subjected to severe corrosion. It is the
case for other underground pipelines, which carry an air, fluid,
oil or gas. The pipes that are generally of mild steel while in
some cases carbon steel, stainless steel or galvanized steel or
rubber lined steels are used for specialized applications. Re-
cently, it was proven that application of cathodic protection Fig. 2. The inner surface of cooling water pipeline after chemical cleaning
system for cooling water systems had reduced the mainte- showing severe corrosion.
262 I. Gurrappa / Journal of Materials Processing Technology 166 (2005) 256–267
Fig. 3. Underground pipeline showing the inner view of the corrosion effect.
undertaken under the supervision of a cathodic protection
engineer. It is important to mention here that poorly de-
signed CP system can do more harms than any benefits,
which it intended to. The most necessary parameters re-
quired to design an effective cathodic protection systems
are:
(i) soil-resistivity,
(ii) pipe line surface area to be protected and
(iii) the current requirement.
4.1.1. Soil-resistivity
This can be established by determining soil-resistivity on
a sample basis across the plant territory and measuring the
corrosivity of soil water extracts. This should be done par-
Fig. 4. Failure of the pipeline due to soil side corrosion at the coating defect.
Fig. 5. Closer view of condenser tube plate showing the severity of corrosion
attack from the water side by corrosive cooling water.
ticularly at the depth at which the pipelines are generally
buried within the plant. As a thumb rule, the underground
pipeline within the plant having soil-resistivity values of less
than 10,000
cm should be routinely provided with exter-
nal corrosion control by using cathodic protection system.
Further, the plants located in the seacoast having sizeable un-
derground piping network invariably require the CP system.
4.1.2. Surface of pipelines
The pipeline surface area to be protected should be known
from the relevant drawings.
4.1.3. Current requirement
The current requirement to obtain uniform protection po-
tential along the cooling water pipelines has to be determined
by actual survey on the piping systems by installing tempo-
rary CP systems. Monitoring of potential at frequent intervals
Fig. 6. Severe corrosion in the inside of condenser water box of mild steel
due to cooling water.
 I. Gurrappa / Journal of Materials Processing Technology 166 (2005) 256–267
after installing the CP is essential to ensure effective protec-
tion.
4.2. Design of cathodic protection system
(a) Having arrived at current requirement necessary for pro-
tection, the next step is to decide which system of ca-
thodic protection should be adopted i.e. sacrificial anodes
or ICCP. This will, however, depend on the limitation of
each method explained earlier.
(b) However, ICCP is universally used for long pipelines.
Also for this system, the control unit/rectifier undoubt-
edly is most suitable equipment for feeding current to
the pipelines, rating of which will depend upon the ac-
tual current requirement survey.
(c) Having decided about the source of supply, the next prob-
lem is of locating the groundbeds/anodes. The position-
ing of anodes on the cooling water system or any other
structure is an important aspect to obtain uniform protec-
tion potentials. As mentioned earlier, a good CP system is
one in which uniform protection potentials are observed
under all operating conditions even under partially paint
damaged condition. It is also important to apply high-
performance anti-corrosive coatings in conjunction with
cathodic protection system for efficient and durable per-
formance of the CP system.
(d) The effectiveness of cathodic protection system should
be checked on all the cooling water systems or buried
pipelines by measuring the potentials with the help of
a portable high-impedance voltmeter and copper/copper
sulphate reference electrode atleast once in a year. It is
more difficult to perform these surveys on submerged
pipelines and therefore, they are usually done for ev-
ery two or three years. Now-a-days, hi-tech systems are
available to check the potentials from above the ground.
(e) Sacrificial anodes can be installed for combating corro-
sion on the inner surfaces of water box and tube plates,
which comes often in contact with highly corrosive cool-
ing waters.
When installing the sacrificial cathodic protection system,
the design should be in such way that the anode should protect
the pipelines for the designed period. The anode life can be
calculated by using the following formula:
M×U
L=
I ×C
where L = anode life in years; M = weight of a single an-
ode (kg); U = utilization factor; I = anode output (Amps);
C = consumption rate (kg/A Y).
(f) For protection of condenser water boxes, magnesium an-
odes can provide good protection over zinc anodes. In or-
der to obtain high-current output the anodes should have
smaller cross section compared to its length.
(g) Dissimilar metals connected to carbon steel such as cop-
per, stainless steel, etc. increase the cathodic protection
263
current requirement because of the less negative poten-
tial that they present to the carbon steel. These metals
should be electrically isolated from the carbon steel even
though they are mechanically connected.
(h) It is important to mention here that corrosion of carbon
steel structure takes place faster under RCC pavement
than the structure under unpaved area because of forma-
tion of galvanic cells between reinforcing bars of RCC
and carbon steel structure. Therefore, necessary precau-
tions have to be taken in order to avoid formation of gal-
vanic cells, which in turn helps in decreasing cathodic
protection current requirement.
4.3. Economics of cathodic protection
When more than thousands of pipelines and million tons
of structures including cooling water systems is in service in
the world today, the means of application of anti-corrosive
devices on buried pipelines and structures and subsequent
saving of an enormous amount of money cannot be over em-
phasized. The estimated annual loss in the year 2000 due to
corrosion is about Rs. 30,000 crores to India while for United
States of America is 275 billion US$. For example, in a par-
ticular cooling water system, a single leak from a pipe can
cause numerous losses and may include:
(i) efficiency loss,
(ii) expensive repairs,
(iii) service interruption and
(iv) contamination of water and thereby changing the chem-
istry of water, etc.
Besides this, once a section of pipeline system starts devel-
oping leaks, experiences have shown that further leaks will
develop at a continuously increasing rate.
For a giant petrochemical complex of worth Rs. 5000
crores located at a very corrosive belt of eastern India,
CP system of worth Rs. 5.35 crores has been installed re-
cently, which is about 0.1% of the total cost. The system
has been installed in the installation stage itself. It is antici-
pated that CP system in conjunction with protective coatings
will prevent occurrence of corrosion of the plant cooling,
fire water lines and the bottom plates of A/G hydrocarbon
storage tanks. As a result, hindrance to plant operation and
safety due to leak formation at these structures are elimi-
nated completely even though the soil is highly corrosive.
In essence, the total cost of cathodic protection system is
about 0.1% of total cost of the plant, which is more econom-
ical in installing the system during commissioning of the
equipment.
4.4. Operation and maintenance
The following practice is recommended for optimum op-
eration and maintenance of the CP system for underground
cooling water-piping systems. It is applicable to other sys-
tems as well.
264 I. Gurrappa / Journal of Materials Processing Technology 166 (2005) 256–267
4.4.1. Recommended operating procedures
(i) The individual anode outputs should be measured,
recorded and adjusted as required until relatively stable
conditions are achieved. This data helps in evaluating
ground bed performance.
(ii) If resistance is added to adjust the anode output, it may
be necessary to adjust the rectifier to restore the required
output.
(iii) The resistance of the groundbed to earth should be cal-
culated periodically. If there is a significant change,
the individual anode output should be adjusted for op-
timum groundbed performance. The results should be
recorded to indicate deterioration of the groundbed
if any.
(iv) The operation of T/R units should be monitored period-
ically. It helps to check the performance of T/R units.
The readers may refer standard textbook for further un-
derstanding the technique [25].
5. Materials selection
The most common method of preventing corrosion effec-
tively is the selection of a proper metal or alloy for a par-
ticular application. Since this is the most important method
of preventing or reducing corrosion damage, one has to
thoroughly investigate the potential alloys with and without
coatings, and choose a proper material in combination with
a suitable design and coating. This process facilitates en-
hancing the life of a component of an equipment/machine,
etc. by many folds and thereby avoids failures during
service.
5.1. High-silicon cast iron
Cast iron is a generic term that applies to high-carbon–iron
steels containing silicon. When the silicon content of grey
cast iron (contains about 2–4% carbon and 1–3% sil-
icon) is increased to over 14%, it becomes extremely
corrosion resistant to many environments. Their inher-
ent hardness makes them resistant to erosion–corrosion.
A newer alloy containing about 3% molybdenum and
chromium is suitable to use in seawater environments be-
cause it improves the pitting corrosion resistance of the
alloy.
The excellent corrosion resistance of high-silicon irons
is due to the formation of a passive SiO2 surface layer
that forms during exposure to the environment. Due to its
high hardness, these alloys are available only in cast forms
for pumps, valves, drain lines and other process equip-
ments. Therefore, high-silicon cast iron, with chromium
and molybdenum, is the most ideal material for fabrica-
tion of cooling water pipelines, water pumps, etc. located
near the seacoast. For other regions, high-silicon cast iron is
sufficient.
5.2. Carbon and low-alloy steels
These steels are based on iron, with about 0.05–1% car-
bon. Low-alloy steels have other alloying elements, at levels
usually below about 2%, mainly for improved mechanical
properties. Carbon and low-alloy steels are relatively inex-
pensive, yet a wide range of strength and hardness can be
obtained by simple variations in carbon content, alloying el-
ements and heat treatment. Carbon and low-alloy steels are
mainly strengthened by the size and distribution of carbide
phases and formation of hard, brittle martensite, when austen-
ite is rapidly cooled from 723◦ C to room temperature. The
normally body centered cubic structure of carbon and low-
alloy steels lead to ductile-to-brittle transition, which limits
usefulness below about −20◦ C.
Carbon and low-alloy steels have relatively low-corrosion
resistance and often require surface engineering techniques
to apply protective coatings, even in relatively non-corrosive
conditions. Coated carbon steels are used extensively for at-
mospheric exposures. Coatings can be omitted only when
carbon steel surfaces are sheltered and dry. Carbon steel is
the material of choice for most pipelines including cooling
water systems and other buried structures. Coatings and ca-
thodic protection are essential for long-term service. Table 3
provides different paints/coatings systems for a variety of
corrosive conditions.
The above table provides only general paints for different
applications. However, various types of other coatings/paints
are available now-a-days. The user has to decide a suitable
coating for his application after consultation with the Corro-
sion Engineer.
High-strength low-carbon steels are used for ship hulls,
offshore drilling platforms and other immersed marine ap-
plications, but coatings and cathodic protection are a must.
The extent of corrosion in marine environments is generally
dependent on access of dissolved oxygen.
Carbon steel is passive in alkaline solutions of high pH
and is used to handle and store such solutions at ambient
temperatures. Carbon steel is used in concrete reinforcement
without coatings, because of alkaline pH in concrete. How-
ever, coatings on reinforcements are sometimes necessary to
control corrosion, when road deicing salts and marine salts
are able to penetrate the protective concrete covering. Thus,
design must provide for adequate thickness of the covering
layer and proper proportions in the concrete mix to minimize
porosity.
Carbon steel is used for tanks and pipes exposed to sul-
phuric acid at concentrations above 65% at ambient tem-
peratures and low velocities below about 0.9 m/s. However,
use is limited above room temperature and excessive flow
or turbulence will disturb the protective sulphate surface film
and cause localized erosion–corrosion. Concentrations below
65% can be stored in carbon steel tanks with anodic protec-
tion, thus avoiding the use of more expensive stainless steel.
Low-alloy steels behave much the same as carbon steels in
aerated neutral water and solutions with corrosion controlled
 I. Gurrappa / Journal of Materials Processing Technology 166 (2005) 256–267
Table 3
Paint systems for different corrosive conditions
Conditions
Dry interiors where structural steel is embedded in concrete, encased in
masonry or protected by membrane or contact type fireproofing
Interior: normally dry, very mild
Exterior: normally dry
Frequently wet by fresh water: involves condensation, splash, spray or
frequent immersion
Frequently wet by salt water: involves condensation, splash or frequent
immersion
Chemical exposure: acidic (pH 5 or lower)
Chemical exposure: neutral (pH 5–10)
Chemical exposure: mild organic solvents, intermittent contact with aliphatic
hydrocarbons, mineral spirits, lower alcohols, glycols, etc.
Chemical exposures: severe includes oxidizing chemicals, strong organic
solvents or combinations of these at high temperature
by dissolved oxygen. However, additions of Cu,Ni,Si and
Cr in the high-strength low-alloy weathering steels improve
atmospheric corrosion significantly. These alloying elements
facilitate the formation during alternate wetting and drying of
an adherent, protective, surface film, which has an agreeable
dark rust colour. The weathering steels have thus been used
successfully in the unpainted condition in applications where
the surface is readily dried by sunlight after periodic wetting
from dew and rain.
5.3. Stainless steels
Iron-based alloys containing atleast 10.5% chromium
are called stainless steels. They are classified as ferritic,
austenitic, duplex, martensitic and precipitation hardening.
The ferritic steels are favoured for use in thin-wall tubing
for heat exchangers where stress corrosion cracking is a con-
cern, i.e. in chemical, petroleum and natural gas processing
industries. The austenitic stainless steels are widely used in
industries. The addition of nickel to iron–chromium alloys
stabilizes the face centered cubic austenite phase and im-
proves corrosion resistance synergistically with chromium.
Corrosion resistance derives from a thin, hydrated, oxidized
chromium-rich, passive surface layer. Chlorides attack the
passive layer and cause pitting, crevice corrosion and SCC.
These problems can be avoided by adding appropriate amount
of molybdenum. Type 304 stainless steel has been used suc-
cessfully for valve parts, pump shaft, fasteners and screens in
fresh water low in chloride. Type 316 stainless steel with 3%
molybdenum content improves resistance to pitting, crevice
and SCC and thus can be used safely in high-chloride envi-
ronments.
The austenitic stainless steels have been used extensively
in the food processing industry, where contamination affect-
ing taste and colour must be avoided. An added advantage is
the easy cleanability of the austenitic stainless steels. Use in
the pharmaceutical industry is similarly widespread, where
contamination is even more critical because dissolved cor-
rosion products may catalyse unwanted biochemical reac-
265
Suggested painting system
Leave unpainted i.e. no paint/coating is required
Latex or one coat (oil-based paints last 10 years or more)
Oil base (oil based paints last 6 years or more)
Vinyl, coal-tar epoxy, epoxy, chlorinated rubber (oil based paints last about
5 years
Vinyl, coal-tar epoxy, epoxy, zinc-rich (oil based paints last about 3 years)
Vinyl
Zinc-rich
Epoxy
Suitable paints only after testing should be applied
tions. The duplex stainless steels find use in more severe
conditions of temperature and chloride content where the
usual austenitic grades are susceptible to pitting, crevice and
SCC.
The martensitic and precipitation hardening stainless
steels are chosen primarily for mechanical strength. Corro-
sion resistance is lower than the other grades of stainless
steels and applications are generally limited to mild environ-
ments. Because of high strength levels, both are susceptible
to hydrogen induced cracking.
5.4. Copper alloys
The thermodynamic tendency for copper corrosion is low
due to its low free-energy content and relatively noble poten-
tials in galvanic series. Thus, copper and its alloys are quite
corrosion resistant in many atmospheric and non-oxidizing
aqueous environments. Ammonia forms complexes with cop-
per and increases general corrosion and stress corrosion
cracking of copper alloys.
Commercially available pure copper is used routinely in
home plumbing systems to handle potable and waste waters
and has excellent resistance to corrosion in soils. The ten-
dency to pitting in some waters has already mentioned earlier
[26]. Atmospheric corrosion resistance is excellent; the char-
acteristic, protective, green CuSO4 forms with time. Copper
sheet roofing has endured for centuries on many historical
buildings and still used for roofing and architectural trim.
The major alloy of copper is brass, formed by the addi-
tions of zinc (10–40%), which improves mechanical proper-
ties by solid solution strengthening and reduces cost of the
alloy. Yellow brass (30% Zn) is most common. Zinc addi-
tions reduce the inherent corrosion resistance of pure copper.
Brasses are vulnerable to SCC, dealloying and impingement
attack or erosion–corrosion. The lower zinc brasses around
10% Zn are much more resistant to SCC and dezincifica-
tion, but strength levels are too low for many applications
and they are more susceptible to impingement attack. Addi-
tions of about 1% Sn–30% Zn brasses form alloys known as
266 I. Gurrappa / Journal of Materials Processing Technology 166 (2005) 256–267
Admiralty metal and Naval Brass respectively, which have
increased resistance to dezincification. Additions of P, As or
Sb (0.02–0.1%) further increase the resistance to dezincifi-
cation. Arsenial aluminium brass (76% Cu, 22% Zn, 2% Al,
0.02%–0.1% As) is resistance to impingement attack and can
be used in seawater condensers and heat exchangers, where
impingement attack is often a problem.
Bronzes are copper alloys containing 8–10% tin, often
with small amounts of phosphorus to improve impingement
attack. The bronzes are more often used in the cast form with
further alloying additions of lead, tin and nickel for seawa-
ter valves, pumps, gears and bushings. Bronzes have rela-
tively better resistance to impingement attack and SCC than
brasses.
Aluminium bronzes are copper, 5–12% aluminium and
alloys that are especially resistant to impingement attack.
Above 8% Al, dealloying of aluminium-rich phases is a
problem. The alloys are susceptible to SCC in many en-
vironments as the brasses, especially ammonia solutions.
Aluminium bronzes are more corrosion resistant than brasses
and are resistant to non-oxidizing mineral and organic acids,
ammonium and alkali metal hydroxides and various natu-
ral waters, including seawater, brackish water and potable
waters.
Copper–nickel alloys are the most corrosion resistant of
the commercial alloys. Alloy 400, with 30% Ni, has max-
imum resistance to impingement attack and SCC, but the
10% alloy often has sufficient resistance at lower cost. Both
have excellent corrosion resistance to non-oxidizing acids,
and find use in the chemical process industries. Their great-
est application, however, is in recirculating steam systems
for condenser and heat exchangers tubing. Amine inhibitors
such as morpholine and hydrazine can decompose in steam
systems to form ammonia, which may cause SCC in many
copper alloys.
6. Designing to prevent corrosion
Design is the first line of defence against corrosion. In-
adequate consideration of corrosion at the design stage of-
ten results in time-consuming and expensive revisions dur-
ing construction and operation. A British survey in the
chemical process industry showed that a majority of cor-
rosion failures were caused by inappropriate design. The
designer must determine materials of construction that are
economical yet provide adequate resistance to the service
conditions.
7. Expert systems
Computer aided programs are available now-a-days to test
and select the suitable material for a particular environment
[27]. Only parameters needed are pipe/component dimen-
sions, environment, life expected, etc. These parameters have
to be fed to get the suitable material with the paint system.
It is possible to predict the corrosion rate of a given mate-
rial in a selective environment. The best way of selecting
the materials is to test them by connecting a cell containing
the material and environment to the computer controlled sys-
tems, and then run the program. The system provides all the
parameters such as current density, corrosion potential, Tafel
constants, corrosion rate, etc. This is a sophisticated system
available now-a-days to test the materials in a given environ-
ment. Based on these studies, expert systems have been made
to select the appropriate material for a selective environment
and are available commercially. However, for newer applica-
tions, the materials have to be tested in the laboratory as well
as in the filed.
Acknowledgements
Defence research and Development Organisation is grate-
fully acknowledged for financial assistance.
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