The Use of Cathodic Protection for Copper Alloys in Seawater Cooling Systems

By Leif Berthagen, ACCEDE Corrosion Engineering, Sweden

(taken from Eurocorr 2001, EFC Working Party meeting. Marine Corrosion)

Historical
In the very early days of coolers and condensers, the water box was normally made
from carbon steel or cast iron. It was a heavy component as the wall thickness was
generous in order to provide a corrosion allowance and was not coated. The water box
served as a sacrificial anode and therefore formed a type of cathodic protection system
for the copper alloy tubes and tube plate as well as dosing iron ions into the water.
The result was excellent and corrosion problems were very limited. The units at this
time tended to be small and the water flow was low.

The next development was to bigger units and coated water boxes. It was at this time
that erosion corrosion started to be observed at the tube plate and tube inlets as the
galvanic protection was lost. In 1912, the Cumberland US patent led to the use of
impressed current cathodic protection to protect against this. Iron blocks were used as
anodes which had the added advantage of providing ferrous ion dosing for the
protection of the inner surfaces down the tubes. Other methods of providing ferrous
ions such as ferrous sulphate dosing and sacrificial anodes followed.

Internationally, the era of building large power plants and steamships took off in the
1950s and 60’s through to 1980. Many large power plants had their own expert in this
area and a number of theories developed in offsetting corrosion issues, particularly as
conditions in the plants differed. These were related to materials, design, type of
cooling water, salinity, content and type of sand/mud, flow velocity and operating
conditions. For the greater part of this time, the copper alloy tube material often used
had been aluminium brass and experience grew relating to safe shut downs, filling
with fresh water, fast cleaning and controlled flow regimes.

In some plants, ferrous ions from ferrous sulphate dosing or iron anodes, cleaning
regimes and cathodic protection systems worked well. However, with time it was
appreciated that care was needed to form a protective layer on the alloy surface. Rate
of surface layer formation depended on the temperature and time of year; formation
rates are faster in warmer waters. In general, and unless there were polluted
conditions, ferrous ion dosing was not so necessary in summer time and iron anodes
could be removed. If the film became too thick, spalling might occur which could
affect flow conditions. During shut downs, if the film dried out, it was necessary to
clean and remove the layers with low concentrations of acid .Acid cleaning combined
with iron dosing and cathodic protection were successfully used to provide good
service at the Danish plant of Aasnes at Kalundborg for many years. The efficiency of
surface layers forming in the tube was checked by measuring the change in outlet
water copper content.

Below 3-4oC, problems were experienced in achieving the protective layers. This was
studied in several Swedish nuclear plants for several years in all kinds of
combinations. Using cathodic protection in the water box, it was possible to prevent
inlet and outlet tube erosion totally; the tubes being protected internally for
approximately 0.5m from the tube plate. The water box, tube plate, rolled ends and
inlet and outlet lengths of tube were successfully protected. The longer tube lengths of
around 10m needed to form the protective layer and this was difficult for aluminium
brass in Scandinavia in wintertime and was eventually solved by changing material.

Today, condensers and cooling systems still use a lot of copper alloys for shipping
and offshore oil/gas production because of cost and also advantages relating to
biofouling resistance. The design advantages related to heat transmission can also be
important. From around 1990, copper-nickels became more widely used for condenser
tubing. Ferrous ions are not so necessary for copper-nickel as aluminium brass. Often,
it is sufficient for impressed current cathodic protection (ICCP) and iron anodes to be
used in the inlet water and inert anodes only in the turn chamber and outlet water box.
Such combinations have been used for a large number of installations with very good
results.

Cleaning
Cleaning is always important for optimising heat transfer whatever the material
combinations used. Today, even if sophisticated automatic pressure regulated filters
are available, they might not be used for smaller installations or sufficient filtering
might not be carried out. In some cases, it is necessary to employ additional
antifouling measures, such as copper ion dosing, as biofouling can be compromised in
copper alloys by applying cathodic protection. Particular problems arise if larger sizes
of shells get stuck in the system, collect silt, and block the tubes causing turbulent
flow and corrosion.

For larger power plants as opposed to shipping, a ball cleaning system is often used
for regular tube cleaning. In the past, soft balls with a layer of carborundum were used
which quickly scratched the aluminium brass surface. Today, too, sometimes heavy
manual cleaning with metal brushes are used and cause problems. Soft nylon brushes
would normally be preferred instead. Automatic brush cleaning systems are available
but often the work is performed using manual brushes and pressurised water and air. It
is important to adhere to instructions given by the heat exchanger or system supplier
as well as methods used for cleaning, and that these are specific to the actual tube
material to be cleaned.

Material Developments and Protection

Materials and alloys have been developed and their performance improved over the
years. Tube materials have changed from copper to aluminium brass to copper-nickel
alloys whereas the stainless steels have changed to higher alloyed alternatives.
Titanium is now used as well. The materials have advantages and disadvantages and
they all have a place in achieving technical and economical solutions.

Cathodic protection of stainless steels or copper-nickel with ICCP can work very well.
Both materials are easy to protect by applying cathodic current and, with clean surface
conditions, only a minor negative polarisation is required to achieve protection (ie 50-
100mV for stainless and even less for copper-nickel). It is more important with lower
grades of stainless steels to have a surface which is clean and free from marine fouling
than for copper-nickel. In general, the current distribution and potential influence can
reach further into stainless steel tubes due to the better oxide resistance than for
copper alloys. Nevertheless good protection results have been achieved for copper-
nickel tubes.
For copper-nickels, it not always necessary, unless the waters are cold or polluted, to
have additional ferrous ions in the sea water to provide protection; it is often used as a
carry over from aluminium brass practice. If used, it is important to keep the
protective layer as thin as possible to reach the optimum corrosion protection and this
is good for heat transfer too. Warmer water (> 15-20oC) might cause an excessive floc
in ordinary sea water, ferrous additions are normally unnecessary as the material will
readily form a protective layer anyway and will show good corrosion resistance
naturally. The addition of an ICCP system will protect the water box and tube plate
from galvanic corrosion or deposit corrosion and the inlet and outlet ends of the tubes
from turbulence or erosion corrosion caused by localised high flow rates. Evaluations
by electrochemical means are not so straight forward or as well understood with
copper alloys as with stainless steel as the protective film formations are different and
the two cannot be compared. Any future development of alternative short term
methods of evaluation suitable for copper alloys to predict the onset of localised
corrosion by erosion or sulphides, would be a bonus.

Past Cathodic Protection Systems

The Cumberland US Patent from 1912 was an important development and this type of
cathodic protection combined with electrolytic iron dosing has been used a lot over
the years mostly in condensers with aluminium brass tubing.

From 1960-1985, a large number of the systems were supplied for both on-shore
power plants and shipping. Many of the big tankers during this period used steam
turbines with large condensers and over a 1000 ships had this type of system. In
Europe, they were often known as BERA systems which was an old trade mark of the
Danish Bergsoe group. The author was involved over a number of years with the
design, supply and service of several hundred of these. The older system used ICCP
and a rectifier unit that supplied a constant voltage or constant direct current output.
To begin with a constant voltage was used but later this changed to a constant current.
Both are possible as the sea water resistivity is normally fairly constant. In some
applications, the system was potentiostatically controlled as well which means
reference electrodes are required leading to increased complexity and more
examination.

However, in practice, the use of reference electrodes in ship installations led to

problems of electrode maintenance. Most of the systems supplied had two current
output settings; one for normal operations and one for stagnant flow which was about
20% of the normal current. Control of the two settings was often by a relay function
with the main cooling water pump. The reason for reducing the current was to avoid
unnecessary consumption of the iron anodes, as well as reducing the amount of
calcareous deposit caused by too low a cathode potential. These white alkaline
deposits can be high in sea water at low potentials and may even block the tubes. The
iron anodes were designed for 1-2 years life. According to Faraday’s Law, the iron is
consumed at approximately 10 kgs per amp.yr. The normal design “rule of thumb” is
that a direct current output of around 1-3amps/m2 of tube plate (depending on flow
and materials) is required to reach a current density to protect the tube in/outlets from
erosion. For example, for a 1m diameter copper-nickel tube plate, a rectifier with a
capacity of 2 amps would be used. As aluminium brass is more sensitive to erosion,
copper-nickel can have the lower current density. Normally, this results in a potential
at the tube plate surface of approx. 1V vs. SCE. Over the years, many studies and data
collection were performed on these installations by ABB/BBC, Stal Laval, EPRI and
others1,2,3,4.

Sacrificial anodes of so called “soft iron” have been used and continue to be so,
particularly in rubber lined water boxes with titanium tubing. Experience where these
ceased to work were when they were completely insulated with a plastic holder and
where steel sheet was used which became passivated by corrosion products. On other
occasions they have been positioned disrupting flow and causing erosion corrosion or
turbulence.

Impressed Current Cathodic Protection Systems Today.

The need for higher water velocities and optimum performance of coolers and their
design has influenced material selection. Today, copper-nickel is frequently selected
and the tubes are rolled tight into the tube plate which may itself be clad with copper-
nickel. In general copper alloys, especially copper-nickel, are very easy to protect by
cathodic protection and only a small cathodic polarisation is required; in normal
favourable conditions this would be about 50mV minimum. Cathodic protection
systems in general are known to be over designed and often too much direct current
output is experienced resulting in heavy alkaline deposits which can increase when a
system is stagnant for part of the time. Different methods have been used to solve this
problem with a variety of success. For more than 10 years an automatic (interrupter
potentiostat) rectifier system has been used in several hundred installations with good
success.

A popular automatic rectifier system uses an interrupter potentiostat and a titanium

mixed oxide coated (activated) anode. The interruption is controlled to less than a
microsecond and the potential (voltage) is read and recorded. In this way, the titanium
oxide anode acts as a reference electrode without a normal reference electrode being
used. This is possible because the noble oxide* coating/activation layer of the
titanium rod versus the water potential is very stable in the first microseconds. This
measurement gives a potential free of voltage (IR) drop. The advantage of this system
is that for periods of stagnant water, the current output is automatically controlled.
Contamination and use of special reference electrodes is avoided as well. The anodic
reaction of oxygen and chlorine gas evolution keeps the anode surface clean.

As these impressed current cathodic protection systems protect the water boxes and
tube inlets and outlets, it is still important that efficient cleaning regimes are practiced
for the bulk length of tubes. Even with a cathodic protection system, it is important to
clean and keep the surfaces free from mud, deposits and fouling. Formation of the
protective layer, commissioning and standby practices need particular attention.
Cathodic protection systems cannot reverse corrosion that has already occurred and
often corrosion of condensers and coolers develops under deposits when the unit is
out of operation and perhaps partially empty of water so that the cathodic protection
cannot function properly. In fact, a standby unit can suffer more from corrosion than
when the unit is under full flow. Standby systems are normally filled with water with
the cathodic protection system on. The water should be periodically circulated, and
replaced with fresh water at least once every week, or drained down and dried. Each
* the type of metal oxide used is dependant on application and whether seawater or brackish water is used.
manufacturer will have their own recommendations and it is important that these are
followed, especially the procedures for unit start up and shut down.

References
1.EPRI Report. Effect of Sulfides, Sand, Temperature and Cathodic Protection on
Corrosion of Condensers. May 1986, CS-4562 Project 1689-3
2.EPRI Report. Effect of Selected Water treatments and Cathodic Protection on
Corrosion and Embrittlement of Condenser Tubes. Jan. 1988, CS-5589 Project 1689-3
3 SVF – 36, 1976. The Influence of Ferrous Sulphate Dosage on the resistance of
Copper alloys to Erosion Corrosion to Baltic Sea water. Henrikson et al.1976
4. SVF – 18, 1975. Corrosion tests in Baltic Sea water on Heat Exchanger Tubes of
Various Metallic Materials. Henrikson and Knutsson. 1975