Desalination 205 (2007) 140146

Corrosion investigation of CuNi tube desalination plant

K. Abouswa*, F. Elshawesh, O. Elragei, A. Elhood
Petroleum Research Center, P. O. Box 6431, Tripoli,Libya
Tel.+214 830022; Fax +214 830031; email: abouswa_2002@yahoo.com

Received 23 February 2006; accepted 1 May 2006

Abstract
Copper-based alloy tubes (i.e. CuNi) are extensively used in desalination plants. This is in order to complete
the heating and evaporating process for the seawater and to obtain distillate water that can be used in the steam
generation plant and as drinking water. A number of these tubes were found to suffer from severe localized corrosion
at 6 oclock position (corrosion throughout the pipe wall thickness). Several samples from the failed tubes were
subjected to metallographic examination and electrochemical test in the simulated working environment (i.e. chloride
content, temp. non evacuated system) in order to establish the main cause of corrosion and failure of the tubes.
Keywords: Condenser tube failure; Pitting corrosion; Multi-stage flash; Desalination plant; Dissolved gases

1. Background
Coppernickel alloys have a remarkable combination of good resistance to both corrosion and
biofouling in seawater. As they are also readily
welded and fabricated, they are an obvious choice
for pipe systems, heat exchangers, boat hulls and
other structures engineered for marine use.
Coppernickels have been specified for seawater use for over 50 years; they are the materials
of first choice for seawater pipe work and con*Corresponding author.

denser service for many of marine applications.

They are used in desalination, power plants and
offshore fire water systems, and for the sheathed
protection of oil and gas platform legs and risers.
Piping of 9010 coppernickel is used for both
natural seawater and hot de-aerated brine service.
Large pipes up to 1.37 m OD are fabricated from
plate; seamless pipe is used for sizes up to about
400 mm.
The multi-stage flash (MSF) process of desalination involves large heat exchangers producing
up to 57,000 m3/d of water. Coppernickel alloys

Presented at EuroMed 2006 conference on Desalination Strategies in South Mediterranean Countries: Cooperation
between Mediterranean Countries of Europe and the Southern Rim of the Mediterranean. Sponsored by the
European Desalination Society and the University of Montpellier II, Montpellier, France, 2125 May 2006.
0011-9164/07/$ See front matter 2007 Elsevier B.V. All rights reserved

K. Abouswa et al. / Desalination 205 (2007) 140146

are widely used to fabricate piping, water boxes,

evaporator shells, tube plates, etc. The 9010 nickel
alloy is usually used in such fabrications, although
a 7030 coppernickel with 2% iron and 2% manganese (C71640, CW353H) is also widely used
for heat exchanger tubing.
2. Coppernickel seawater corrosion resistance
The resistance to seawater corrosion of coppernickel alloys results from the formation of a
thin, adherent, protective surface film which forms
naturally and quickly on exposure to clean seawater. The film is complex and predominantly cuprous oxide with the protective value enhanced by
the presence of nickel and iron. The initial film
forms fairly quickly over the first couple of days
but takes up to three months to fully mature. This
initial exposure is crucial to the long-term performance of coppernickel [14].
Once a good surface film forms, the corrosion
rate will continue to decrease over a period of
years. For this reason, it has always been difficult
to predict the life of coppernickel alloys based
on short-term exposures. Normally, corrosion rates
of 0.020.002 mm/y are anticipated.
3. Role of flow rates
With increasing seawater flow rate, corrosion
remains low due to the resilience of the protective
surface film [2]. But when the velocity for a given
geometry is such that the shear stress action of
the seawater on the film is sufficient to damage it,
impingement attack can result. General experience
has shown that 9010 coppernickel can successfully be used in condensers and heat exchangers
with velocities up to 2.5 m/s; the 7030 alloy can
be used up to 3 m/s. For pipeline systems, higher
seawater velocities can safely be used in larger
diameter pipes as indicated by BS MA18. Salt
water piping systems in ships which suggested a
maximum design velocity of 3.5 m/s in pipes of
100 mm and larger for 9010 coppernickel, and

141

4 m/s for the 7030 alloy. Although these guideline values are now considered to be conservative,
they work well because they take into account effects from things like bends which cause areas of
high local flow rate. Nevertheless, extreme turbulence has to be avoided from elements like tight
radius bends, partial blockages and areas downstream of partially throttled valves.
Minimum flow rates of more than 1 m/s are
usually preferred to avoid sediment build up.

4. Localized corrosion
Coppernickels have good inherent resistance
to chloride pitting and crevice corrosion. Crevice
corrosion is seldom found. The mechanism is a
metal ion concentration cell type totally different
to that of stainless steels. Coppernickels are not
susceptible to chloride or sulphide stress corrosion
cracking or hydrogen embrittlement and unlike
brasses do not suffer cracking due to ammonia in
seawater service. But ammonia can cause higher
corrosion rates, although coppernickels are more
resistant than many other copper-based alloys.
Coppernickel tubing is resistant to chlorination
at the dosing levels used to control biofouling.
Excessive chlorination can be detrimental, as it
reduces erosion-corrosion resistance.
Dealloying is not common with coppernickel
alloys. De-nickelification of the 7030 alloy has
been encountered occasionally in refinery overhead condenser service, where hydrocarbon
streams condense at temperatures above 150C.
This appears to be due to thermo-galvanic effects
resulting from local hot spots. The solution has
been to remove the deposits which lead to the hot
spots either by more frequent cleaning or by increasing flow rates. Ammonia in seawater can
produce a type of de-alloying which looks similar
to hot spot corrosion. This happens at around
ambient temperature, but only under heat transfer
conditions. It can be controlled by adding ferrous
sulphate to the seawater.

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K. Abouswa et al. / Desalination 205 (2007) 140146

5. Corrosion failure investigation

5.2. Low magnification microscopy

5.1. Visual investigation

External and internal examination on the failed

tube was carried out using low magnification microscope. Fig. 2ab shows the extent of the corrosion pits observed on the external tube surface.
Pits were isolated and some were of cluster type
encountered CuNi tubes at the lower part of tube
bundle.
A sign of some corrosion products and scale
like were visible around the pits. Some pits were
found to be covered with the while corrosion products.

Visual investigation of the corroded tube

revealed the presence of several corrosion pits
with different morphology and size as shown in
Fig. 1ab, few external pits throughout the wall
thickness were visible. Corrosion hole on the
external surface of the tube is clearly shown in
Fig. 1a. Cluster of small corrosion pits on the
lower part of tube bundle can be observed clearly
in Fig. 1b.

Fig. 1. Large hole (a) and cluster of small corrosion pits (b).

a
Fig. 2. Localized corrosion pits.

K. Abouswa et al. / Desalination 205 (2007) 140146

5.3. Chemical analysis

Chemical analysis of CuNi tubes was conducted using SEM-EDAX and the results confirm
that the tubes were made of CuNi (9010 alloy).
The added iron was found to be less than 2.0 wt%.
This was confirmed by the ferrite-scope meter.
These results exclude the role of iron in the
corrosion mechanism and tubes failure.
5.4. Investigation using SEM
Detailed examination of the failed CuNi tubes
using SEM confirms the observation obtained
from the optical microscopic examination. The
morphology of corrosion pits on the external tubes
surface was found to be different as shown in
Fig. 3ab. Some pits were found to be shallow,
others were narrow and deep while most were
wide and shallow. Many of pits were penetrated
throughout the pipe wall thickness. Few pits regular in shape and large in size penetrated throughout
the wall thickness were visible.
The analysis of the corrosion products and
scales precipitated on the tube revealed the presence of a complex of compounds composed of
cuprous oxide, CuCl and cupric oxide, as shown
in Table 1. This was confirmed by the results of

143

Table 1
Results of XRD analysis
Elements

Concentration (wt. %)

C
O
Cu
Mg
Si
Cl
Fe
Ni

2.22
27.00
51.32
0.077
0.138
9.365
1.949
7.459

XRD analysis. A sign of chloride, Mg, high oxygen and carbon were detected in the analyzed thin
film scale, this indicates that the tubes were exposed directly to seawater vapor. The heavy scale
was observed on the stainless steel demisters and
surrounding areas.
5.5. Electrochemical tests
Electrochemical study using potentiodynamic
test technique was conducted on samples taken
from the failed CuNi tubes in the environment
containing a wide range of chloride ions, air and
some of CO2 gas. The latter was made to simulate

a
Fig. 3. Wide and shallow pits penetrated throughout the wall thickness.

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K. Abouswa et al. / Desalination 205 (2007) 140146

the real condition when the vacuum system was

not properly working.
Samples of 1 cm2 exposure area were prepared
for this study and tested in the simulated test environment. CuNi samples were tested in solutions with different chloride concentration (100,
1000, 22,000 and 35,000 ppm) with addition of
blown air in one case and some CO2 in another
case. The latter were added in order to simulate
the real environment when the vacuum system
does not working properly. The tests were carried
out at room temperature (RT) and 70C.
Fig. 4 shows that the corrosion potential of Cu
Ni alloys is markedly affected by the chloride concentration. This was evident when tests were conducted at a chloride concentration of 1000 ppm at
70C under static condition.
Fig. 5 shows the role of CO2 gas present within
seawater on the CuNi tubes at RT and 70C. The
results showed detrimental effect of CO2 on the
corrosion potential particularly at 70C. Low
potential of (250 mV) was recorded.

Fig. 6 shows the role of seawater or when

22,000 ppm of chloride ions are present on the
CuNi tubes alloy when tests were carried out in
open air and when the air was blown into the test
cell.

Fig. 5. Polarization curves of CuNi alloy in seawater

with and without CO2 at (RT) and at 70C.

Fig. 4. Polarization curves of CuNi alloy in distilled

water with CO2 at (RT) and at 70C at different concentration of Cl.

Fig. 6. Polarization curves of CuNi alloy in seawater

open to air and blowing air at 70C.

K. Abouswa et al. / Desalination 205 (2007) 140146

6. Discussion
The results of examination and tests conducted
on CuNi tubes for the desalination revealed the
fact that the corrosion was localized and initiated
from the external surface.
The mechanism of failure can be given as follows: the results of visual and microscopic examination revealed the fact that the corrosion was
initiated externally on the CuNi tubes. Several
localized corrosion pits (isolated and clustered)
were observed on the examined tubes at 6 oclock
position. SEM-EDAX analysis of the corrosion
products and deposit was found to compose of
cuprous oxide, high oxygen and carbon content.
The high carbon content may be from build-up of
scale (carbonate-HCO3), as a result of CO2 gas
present within the system (dissolved within the
water droplets), particularly when the vacuum
system does not working properly.
The conducted examinations on the received
tubes excluded the suggestion that the CuNi
material composition was the main cause of Cu
Ni tubes failure. The results of chemical analysis
confirm that the tubes were made of CuNi alloy
(9010).
The mechanism of Cu-Ni tubes corrosion and
failure could be attributed to the process control
problem which can be given as per these two
scenarios.
6.1. Scenario I
i

Deposition of seawater droplets or water vapor

droplets carrying some chloride ions on Cu
Ni tubes. This may occur when the demister
unit was not in the right position.
ii Leakage of one or more tubes as a result of
internal corrosion. This may lead to deposition
of seawater salts on CuNi tubes.
One of the above scenarios has led to build-up
of non continuous film-like scale on CuNi tubes.
This was evident from microscopic observation
and conducted examination using SEM-EDAX
analysis, as shown in Figs. 2 and 3. Carbon, oxy-

145

gen, some chloride ions, K and Na, were all detected at areas around the localized corrosion sites
(pits).
The present thin film of scale may have created
corrosion micro-cells leading to autocatalytic
progressive in the corrosion process [1]. The corrosion process is aggravated by surrounding temperature in addition to the presence of chloride ions
within the build-up thin scale (salts, carbonates
result of CO2 and water). The presence of this film
in wet condition in addition to the dissolved gases
CO2 and O2 is expected to aggravate the corrosion
process via formation of carbonic acid and reduction of pH.
The conducted electrochemical tests confirmed
that CO2 gas alone seem to be not enough to cause
severe or localized corrosion on CuNi tubes/
material and the chloride ions in concentration
more than 100 ppm need to be present, as shown
in Fig. 4. The corrosion was found to be pronounced when the chloride ions concentration was
found to be more than 1000 ppm in presence of
CO2 as shown in Fig. 5. Highest corrosion rate
was expected when high concentration of chloride
ions (22,000 ppm Cl ions H seawater) was present
along with CO2 gas as shown in Figs. 46. The
requirements to chloride ions may be due to the
fact that pH was not low enough to cause corrosion.
6.2. Scenario II
The other suggested mechanism can be given
as follows:
The effect of vapor side environment is expected to play some role in Cu-Ni tube corrosion.
The surrounded environment is steam contains
CO2 and oxygen gases [1]. The non condensable
CO2 gas is expected to form low pH carbonic acid,
in the vapor zone leading to increased vapor side
corrosion (VSC).
As mentioned above, most desalination units
have inadequate venting system (small, not efficient etc.) and some gas like CO2 and oxygen is
expected within the system. The condensed vapor

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K. Abouswa et al. / Desalination 205 (2007) 140146

droplets on tubes are expected to contain CO2 gas

in addition to oxygen. As per tube bundle design
the water droplets with incondensable bubbles of
CO2 are expected to persist in the lower part of
tube bundle at cold end tube sheet. This allows
enough sub-cooling for water droplet and reduction in pH sufficiently for corrosion to occur particularly when enough air is present.
7. Conclusions
1. The severe corrosion of CuNi tubes after
they have been in service for a long period of time
can be attributed to the process control problem.
It seems that quite a large amount of seawater was
evaporated and precipitated as film-like scale on
the external surface of CuNi tubes. This may
generate corrosion micro-cells which in turn act
as a potential site for localized corrosion to proceed particularly when gases such as CO2 and O2
are present within the condensed water on CuNi
tubes. The later reduce pH and enhance the corrosion attack in a short period of time.
2. Alternative conclusion of CuNi tubes corrosion is that the condensation of water droplets
on CuNi tubes contains non condensable CO2
gas and oxygen can be the main cause of tube
corrosion and failure. The marked reduction in
pH of condensed water droplets condensed on Cu
Ni will enhance and accelerate the corrosion process.

8. Recommendations
1. Identify the source of seawater salts found
on CuNi tubes as a result of internal corrosion
leakage or as a result of demister/vacuum problem.
The presence of chloride ions was confirmed by
EDAX analysis.
2. Check the performance of the vacuum system of the desalination unit(s). This is an important
step and need to be considered. Presence of gases
shall assist in initiation and acceleration in the corrosion process.

References
[1] G.J. Danek and R.B. Niederberger, Accelerated
corrosion of coppernickel alloys in polluted waters,
Corrosion/76, Paper No.76, NACE, 1976.
[2] A. Syrett, Accelerated corrosion of copper in flowing
pure water contaminated with oxygen and sulfide,
Corrosion, 33 (1977) 257262.
[3] C. Giulani and G. Bombard, Influence of pollution
on the corrosion of copper alloys in flowing salt
water, Br. Corrosion J., 8 (1973) 2024.
[4] R. Dooly and J. Glater, Alkaline scale formation in
boiling sea water brines, Desalination, 11 (1972) 1
16.
[5] M.A. Finan and M.N. Elliot, A theory of the formation of magnesium scales in sea water distillation
plants, and means for their prevention, Desalination,
14 (1974) 325340.