Desalination 205 (2007) 140–146

Corrosion investigation of Cu–Ni 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. Cu–Ni) 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 o’clock 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 denser service for many of marine applications.

They are used in desalination, power plants and
Copper–nickel alloys have a remarkable com-
offshore fire water systems, and for the sheathed
bination of good resistance to both corrosion and
protection of oil and gas platform legs and risers.
biofouling in seawater. As they are also readily
Piping of 90–10 copper–nickel is used for both
welded and fabricated, they are an obvious choice
natural seawater and hot de-aerated brine service.
for pipe systems, heat exchangers, boat hulls and
Large pipes up to 1.37 m OD are fabricated from
other structures engineered for marine use.
plate; seamless pipe is used for sizes up to about
Copper–nickels have been specified for sea-
400 mm.
water use for over 50 years; they are the materials
The multi-stage flash (MSF) process of desali-
of first choice for seawater pipe work and con-
nation involves large heat exchangers producing
up to 57,000 m3/d of water. Copper–nickel alloys
*Corresponding author.

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, 21–25 May 2006.

0011-9164/07/$– See front matter © 2007 Elsevier B.V. All rights reserved
 K. Abouswa et al. / Desalination 205 (2007) 140–146
are widely used to fabricate piping, water boxes,
evaporator shells, tube plates, etc. The 90–10 nickel
alloy is usually used in such fabrications, although
a 70–30 copper–nickel with 2% iron and 2% man-
ganese (C71640, CW353H) is also widely used
for heat exchanger tubing.
2. Copper–nickel seawater corrosion resistance
The resistance to seawater corrosion of cop-
per–nickel alloys results from the formation of a
thin, adherent, protective surface film which forms
naturally and quickly on exposure to clean seawa-
ter. The film is complex and predominantly cup-
rous 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 per-
formance of copper–nickel [1–4].
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 copper–nickel alloys based
on short-term exposures. Normally, corrosion rates
of 0.02–0.002 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 90–10 copper–nickel can success-
fully be used in condensers and heat exchangers
with velocities up to 2.5 m/s; the 70–30 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 90–10 copper–nickel, and
141
4 m/s for the 70–30 alloy. Although these guide-
line values are now considered to be conservative,
they work well because they take into account eff-
ects from things like bends which cause areas of
high local flow rate. Nevertheless, extreme tur-
bulence has to be avoided from elements like tight
radius bends, partial blockages and areas down-
stream of partially throttled valves.
Minimum flow rates of more than 1 m/s are
usually preferred to avoid sediment build up.
4. Localized corrosion
Copper–nickels 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. Copper–nickels 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 copper–nickels are more
resistant than many other copper-based alloys.
Copper–nickel 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 copper–nickel
alloys. De-nickelification of the 70–30 alloy has
been encountered occasionally in refinery over-
head condenser service, where hydrocarbon
streams condense at temperatures above 150°C.
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 in-
creasing 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.
142 K. Abouswa et al. / Desalination 205 (2007) 140–146

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 mic-
Visual investigation of the corroded tube
roscope. Fig. 2a–b shows the extent of the corro-
revealed the presence of several corrosion pits
sion pits observed on the external tube surface.
with different morphology and size as shown in
Pits were isolated and some were of cluster type
Fig. 1a–b, few external pits throughout the wall
encountered Cu–Ni tubes at the lower part of tube
thickness were visible. Corrosion hole on the
bundle.
external surface of the tube is clearly shown in
A sign of some corrosion products and scale
Fig. 1a. Cluster of small corrosion pits on the
like were visible around the pits. Some pits were
lower part of tube bundle can be observed clearly
found to be covered with the while corrosion pro-
in Fig. 1b.
ducts.

a b

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

a b
Fig. 2. Localized corrosion pits.
 K. Abouswa et al. / Desalination 205 (2007) 140–146 143

5.3. Chemical analysis Table 1

Results of XRD analysis
Chemical analysis of Cu–Ni tubes was con-
ducted using SEM-EDAX and the results confirm Elements Concentration (wt. %)
that the tubes were made of Cu–Ni (90–10 alloy). C 2.22
The added iron was found to be less than 2.0 wt%. O 27.00
This was confirmed by the ferrite-scope meter. Cu 51.32
These results exclude the role of iron in the Mg 0.077
corrosion mechanism and tubes failure. Si 0.138
Cl 9.365
Fe 1.949
5.4. Investigation using SEM Ni 7.459
Detailed examination of the failed Cu–Ni tubes
using SEM confirms the observation obtained
from the optical microscopic examination. The
XRD analysis. A sign of chloride, Mg, high oxy-
morphology of corrosion pits on the external tubes
gen and carbon were detected in the analyzed thin
surface was found to be different as shown in
film scale, this indicates that the tubes were ex-
Fig. 3a–b. Some pits were found to be shallow,
posed directly to seawater vapor. The heavy scale
others were narrow and deep while most were
was observed on the stainless steel demisters and
wide and shallow. Many of pits were penetrated
surrounding areas.
throughout the pipe wall thickness. Few pits regu-
lar in shape and large in size penetrated throughout
5.5. Electrochemical tests
the wall thickness were visible.
The analysis of the corrosion products and Electrochemical study using potentiodynamic
scales precipitated on the tube revealed the pre- test technique was conducted on samples taken
sence of a complex of compounds composed of from the failed Cu–Ni tubes in the environment
cuprous oxide, CuCl and cupric oxide, as shown containing a wide range of chloride ions, air and
in Table 1. This was confirmed by the results of some of CO2 gas. The latter was made to simulate

a b
Fig. 3. Wide and shallow pits penetrated throughout the wall thickness.
144 K. Abouswa et al. / Desalination 205 (2007) 140–146

the real condition when the vacuum system was Fig. 6 shows the role of seawater or when
not properly working. 22,000 ppm of chloride ions are present on the
Samples of 1 cm2 exposure area were prepared Cu–Ni tubes alloy when tests were carried out in
for this study and tested in the simulated test en- open air and when the air was blown into the test
vironment. Cu–Ni samples were tested in solu- cell.
tions 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 70°C.
Fig. 4 shows that the corrosion potential of Cu–
Ni alloys is markedly affected by the chloride con-
centration. This was evident when tests were con-
ducted at a chloride concentration of 1000 ppm at
70°C under static condition.
Fig. 5 shows the role of CO2 gas present within
seawater on the Cu–Ni tubes at RT and 70°C. The
results showed detrimental effect of CO2 on the
corrosion potential particularly at 70°C. Low
potential of (–250 mV) was recorded.
Fig. 5. Polarization curves of Cu–Ni alloy in seawater
with and without CO2 at (RT) and at 70°C.

Fig. 4. Polarization curves of Cu–Ni alloy in distilled Fig. 6. Polarization curves of Cu–Ni alloy in seawater
water with CO2 at (RT) and at 70°C at different concen- open to air and blowing air at 70°C.
tration of Cl–.
 K. Abouswa et al. / Desalination 205 (2007) 140–146 145

6. Discussion gen, some chloride ions, K and Na, were all detect-
ed at areas around the localized corrosion sites
The results of examination and tests conducted
(pits).
on Cu–Ni tubes for the desalination revealed the
The present thin film of scale may have created
fact that the corrosion was localized and initiated
corrosion micro-cells leading to autocatalytic
from the external surface.
progressive in the corrosion process [1]. The cor-
The mechanism of failure can be given as fol-
rosion process is aggravated by surrounding temp-
lows: the results of visual and microscopic exa-
erature in addition to the presence of chloride ions
mination revealed the fact that the corrosion was
within the build-up thin scale (salts, carbonates
initiated externally on the Cu–Ni tubes. Several
result of CO2 and water). The presence of this film
localized corrosion pits (isolated and clustered)
in wet condition in addition to the dissolved gases
were observed on the examined tubes at 6 o’clock
CO2 and O2 is expected to aggravate the corrosion
position. SEM-EDAX analysis of the corrosion
process via formation of carbonic acid and reduc-
products and deposit was found to compose of
tion of pH.
cuprous oxide, high oxygen and carbon content.
The conducted electrochemical tests confirmed
The high carbon content may be from build-up of
that CO2 gas alone seem to be not enough to cause
scale (carbonate-HCO3), as a result of CO2 gas
severe or localized corrosion on Cu–Ni tubes/
present within the system (dissolved within the
material and the chloride ions in concentration
water droplets), particularly when the vacuum
more than 100 ppm need to be present, as shown
system does not working properly.
in Fig. 4. The corrosion was found to be pro-
The conducted examinations on the received
nounced when the chloride ions concentration was
tubes excluded the suggestion that the Cu–Ni
found to be more than 1000 ppm in presence of
material composition was the main cause of Cu–
CO2 as shown in Fig. 5. Highest corrosion rate
Ni tubes failure. The results of chemical analysis
was expected when high concentration of chloride
confirm that the tubes were made of Cu–Ni alloy
ions (22,000 ppm Cl ions H– seawater) was present
(90–10).
along with CO2 gas as shown in Figs. 4–6. The
The mechanism of Cu-Ni tubes corrosion and
requirements to chloride ions may be due to the
failure could be attributed to the process control
fact that pH was not low enough to cause corro-
problem which can be given as per these two
sion.
scenarios.
6.2. Scenario II
6.1. Scenario I
The other suggested mechanism can be given
i Deposition of seawater droplets or water vapor
as follows:
droplets carrying some chloride ions on Cu–
The effect of vapor side environment is ex-
Ni tubes. This may occur when the demister
pected to play some role in Cu-Ni tube corrosion.
unit was not in the right position.
The surrounded environment is steam contains
ii Leakage of one or more tubes as a result of
CO2 and oxygen gases [1]. The non condensable
internal corrosion. This may lead to deposition
CO2 gas is expected to form low pH carbonic acid,
of seawater salts on Cu–Ni tubes.
in the vapor zone leading to increased vapor side
One of the above scenarios has led to build-up corrosion (VSC).
of non continuous film-like scale on Cu–Ni tubes. As mentioned above, most desalination units
This was evident from microscopic observation have inadequate venting system (small, not effi-
and conducted examination using SEM-EDAX cient etc.) and some gas like CO2 and oxygen is
analysis, as shown in Figs. 2 and 3. Carbon, oxy- expected within the system. The condensed vapor
146 K. Abouswa et al. / Desalination 205 (2007) 140–146
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 reduc-
tion in pH sufficiently for corrosion to occur par-
ticularly when enough air is present.
7. Conclusions
1. The severe corrosion of Cu–Ni 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 Cu–Ni tubes. This may
generate corrosion micro-cells which in turn act
as a potential site for localized corrosion to pro-
ceed particularly when gases such as CO2 and O2
are present within the condensed water on Cu–Ni
tubes. The later reduce pH and enhance the corro-
sion attack in a short period of time.
2. Alternative conclusion of Cu–Ni tubes cor-
rosion is that the condensation of water droplets
on Cu–Ni 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 pro-
cess.
8. Recommendations
1. Identify the source of seawater salts found
on Cu–Ni 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 sys-
tem 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 cor-
rosion process.
References
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corrosion of copper–nickel 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,
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[3] C. Giulani and G. Bombard, Influence of pollution
on the corrosion of copper alloys in flowing salt
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[4] R. Dooly and J. Glater, Alkaline scale formation in
boiling sea water brines, Desalination, 11 (1972) 1–
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[5] M.A. Finan and M.N. Elliot, A theory of the forma-
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