Corrosion Resistance of Cupronickels - An Overview PDF

CORROSION RESISTANCE OF
CUPRONICKELS - AN OVERVIEW
J. Mathiyarasu, N. Palaniswamy and V.S. Muralidharan
Corrosion Science and Engineering Division,

Central Electrochemical Research Institute,
Karaikudi - 630 006, India
CONTENTS
Abstract
1. Introduction
2. Physico-Chemical Properties of Copper-Nickel Alloys
3. Oxidation of Copper-Nickel Alloys
4. Electrochemical Behaviour of Copper-Nickel Alloys
5. Corrosion Resistance Behaviour of Copper Nickel Alloys
5.1. Atmospheric Corrosion
5.2. Corrosion Behaviour in Aqueous Solutions
5.2.1. In Chloride Solutions
5.2.2. In Acidic Solutions
5.2.3. In Alkaline Solutions
5.3. Corrosion in Marine Environment
5.3.1. Effect of Oxygen Content
5.3.2. Effect of Temperature
5.3.3. Effect of Velocity
5.3.4. Effect of Pollutants
5.3.4.1. Sulphide Pollution
5.3.4.2. Ammonia Pollution
5.4. Effect of Fouling and Microbial Corrosion
6. Preventive or Remedial Measures
7. Conclusions
Acknowledgement
References
Brought to you by | Purdue University Libraries

Authenticated
65
Download Date | 5/26/15 4:04 PM
Vol. 18, No. 1, 2000 Corrosion Resistance of Cupronickels-
An Overview
ABSTRACT
Cupronickel alloys have been extensively used in marine and offshore

applications. These alloys offer desirable physical and mechanical properties
to be used as a versatile engineering alloy. The oxidation resistance of these
alloys was due to the formation of scales consisting of a thick, inner C u 2 0
layer and a thin, outer CuO layer, together with nickel rich internal oxide.
These alloys are superior to bronzes in their corrosion resistance but fail
under oxidising conditions. In sulphide atmospheres they undergo sulphidi-
zation. Depending upon the alloy composition, they form layers consisting of
alloy/nickel sulphide/CuS of various proportions. In chloride solutions, they
undergo localised attack. For lower chloride concentration, an increase in
nickel content worsens the resistance to passive film breakdown, where as for
higher chloride concentration an increase in the nickel content favour
passivation.
In seawater, the prime source is dissolved oxygen and the corrosion
product is Cu 2 0. This is formed by the hydrolysis of CuCl2". The use of
ozone enhanced the dissolved oxygen content. Localised attack occurred at
those points where the seawater is in motion. The impingement and general
corrosion resistance was improved by the addition of iron in the alloy.
Sulphides and ammonia as pollutants adversely influenced the performance
of the alloy. Microbial adhesion alters the protective properties of the
complex layers of the alloy. The bacteria enhanced the corrosion rates in
seawater with intergranular corrosion and denickelification. The minor
additions of an element, use of inhibitors in the medium and cathodic
protection are the main methods of corrosion control in aqueous media.
The various aspects of the corrosion resistance behaviour of cupronickel
alloys in different environments are discussed in the review.
1. INTRODUCTION
Copper and its alloys have been extensively used to fabricate structures
and components exposed to seawater and other marine environments because
of their low corrosion susceptibility III. Among those, copper-nickel alloys
are widely commercially used because they exhibit good corrosion and
biofouling resistance in marine environments. Cupronickels were introduced
for marine application mainly for condenser tubing, where good resistance to

66 Authenticated
J. Mathiyarasu et al. Corrosion Reviews
localised (pitting) and erosion corrosion is important. Over the last few
decades the use of cupronickels has been extended to ship and boat hulls,
offshore structures 121, expanded mesh for fish cages and intake screens at
power stations /3/.
The corrosion rates of cupronickels decrease sharply with increasing
nickel content (up to ~ 40 wt.%) and thereafter remain approximately
constant /4/. The highest corrosion resistance was observed for nickel content
40-50% 151. The corrosion behaviour is strongly dependent on the nature and
characteristics of the passive film formed on the alloy /6-8/. However, these
alloys suffer greatly accelerated corrosion where exposed to seawater. The
main corrosion hazard for cupronickels in seawater can be related to the
presence of chloride. However, in polluted environment two other factors
must be taken into account; viz. the presence of sulphide anions and the
presence of organisms which are capable of fouling on the surface. Another
frequent cause of corrosion in marine environments has been attributed to
organic materials present in pollutes and stagnant seawater in harbour areas
191. Localised attack occurs due to the combined effects of corrosion and
erosion (impingement attack) as a consequence of the removal of passive film
by turbulent water flow /10/.
The extensive uses of cupronickels in marine and offshore application led
to considerable research on corrosion in seawater, at various conditions of
temperature, aeration, alloy containing varying amounts of nickel and other
alloying elements. Thus an overview of several works revealed complex
electrochemical behaviour in polluted saline media where the corrosion
behaviour of cupronickels can be altered by the simultaneous presence of
chlorides, sulphides and biofilm formation and its detachment. This paper
reviews various aspects of the corrosion behaviour of the cupronickels
covering several recent surveys and reports of documents.
2. PHYSICO-CHEMICAL PROPERTIES
Alloys of copper with nickel are called cupronickels with nickel

concentrations ranging from 2.5 to 30%. Copper and nickel form
homogeneous solid solutions at all concentrations. The phase diagram of
copper-nickel system / l l / suggests the formation of single-phase (ß-phase)
solid solution. The cupronickels may be classified as,

Authenticated
67
An Overview
1. The cupronickels which contain 20 to 30 % nickel, remainder copper,

with up to 2 % Fe or Mn modifiers.
2. The Cu/Ni/Fe alloys which are found commercially in two ranges - the
5% nickel and 10% nickel with remainders as, except for Fe addition
ranging from 1-2% depending on the nickel content.
3. The nickel-copper alloys in which the % of nickel exceeds that of copper.
The strength and hardness of these alloys increase with nickel content,
approaching the strength of ferrous alloys. Their modulus of elasticity also
increases with nickel content. These alloys cannot be hardened by heat
treatment, but they exhibit considerable increase in hardness on cold
working.
The small additions (0.5 to 1%) of modifiers improve their corrosion
resistance in seawater. Thus alloys containing iron and manganese are called
admiralty cupronickels. The addition of iron to the alloy results in the
formation of a film that is very resistant to the impingement attack caused by
high-speed water. This film also provides good protection against attack by
polluted brackish water and water that may be stagnant for long periods of
time in the tubes. The beneficial effect of iron addition has been summarised
earlier by several authors /12-16/.
The most widely used alloys are the 70/30 and 90/10 varieties to which
additions such as Fe and Mn are made. Iron modified alloy has the greatest
tolerance for high velocity effects. Stewart and LaQue /17/ suggested that the
iron in cupronickels form hydrated iron oxides in the corrosion product
thereby improving its protective action. The addition of manganese helps to
control the rate of precipitation in aluminium hardened cupronickels.
Cupronickel 70/30 alloys with iron and manganese contents of at least 0.5%
have high abrasion resistance. Alloys without the addition of iron improve
the resistance to velocity effects. The division between alloys that foul and
those do not occur at 30 to 40% nickel. When iron is added to the extent of
about 0.3 to 0.5% in 70/30 alloy, resistance to fouling is greatly reduced. The
10% nickel alloy containing 1-2% iron can be expected to remain free from
fouling.
Beccaria and Crousier /18/ reported that the effect of iron addition on
70/30 alloy increased the average corrosion resistance of the alloy. This
beneficial effect is due to the formation of a layer containing large quantity of
nickel and iron oxides. A disadvantage of iron addition is the possibility of

68 Authenticated
pit and crevice formation as a result of segregation of nickel-iron rich

precipitates at grain boundaries.
The physical and mechanical properties (Table-1) /19/ of the cupronickel
alloys are quite similar to those of the corresponding brasses. But the
corrosion resistance of cupronickels is superior to that of bronzes. The
optimum iron content for cupronickels is between 1.0 and 1.5 %. The amount
of iron found in commercial tubes varies with the makers and the country of
origin. Iron segregation occur in these alloys during hot working in the range
600-650°C and this can affect the corrosion and corrosion-erosion resistance.
The iron segregation evened out by heating to 750°C; and air-cooling does
not result in resegregation. Quenching is liable to cause the formation of
micro-cracks and may cause corrosion fatigue.
Table-1
Physical and mechanical properties of cupronickels /19/
Properties 80/20 alloy 70/30 alloy

Melting point °c 1200 1225
Density at 20°C g/cc 8.94 8.94
Electrical conductivity 6 5
Thermal conductivity 22 17
Tensile strength (soft) 50,000 55,000
(hard) 90,000 95,000
Yield point soft, psi 23,500 23,500
3. O X I D A T I O N OF C O P P E R - N I C K E L A L L O Y S
The rate of oxidation of cupronickels (up to 3 0 % nickel) is not

appreciably different from that of pure copper in the temperature range
750-950°C /20/. The extent of oxidation of copper-nickel alloys, one hour in
air at 800-1000°C, is given in Fig. 1 /20/. Above 30% nickel, the rate of
oxidation decreases with the increase in nickel content. Levin and Wagner
/21/ studied the oxidation of a 62% copper - 38% nickel alloy at 800°C in
pure oxygen. A parabolic rate constant of 1.4 χ 10" 7 g 2 /(cm 4 )(min) was
observed. Annealing the sample for 4 hours in argon after oxidation had
proceeded for 30 min. resulted in a significant reduction in the rate constant.

69
Authenticated
An Overview
10
-C
\
10
ε iooo'C
Ε
0-1
0-01
0 20 AO SO 80 100
% NICKEL
Fig. 1: Oxidation of copper-nickel alloys /20/.
The change in rate upon annealing was attributed to equilibrium in the oxide
by the reaction,
Ni(in alloy) + C u 2 0 -> NiO + 2Cu
and a resultant change in diffusion of ions through the new oxide. The
extended scale present on a 7% nickel alloy oxidised at 300-700°C consists
entirely of copper oxides 1221. After removal of this outer scaling layer, a
brown layer lying under the surface was identified as NiO on the basis of
lattice constants determined by electron diffraction analysis.
The oxidation of cupronickel 60/40 alloy at temperatures up to 650°C
forms thick oxides, which contains invariably copper oxide /23/. Yet at room
temperature the oxide film is entirely nickel oxide. The overgrowth of the
initial nickel oxide by cuprous oxide takes place on 60/40-cupronickel alloy.
The physical and chemical displacement reaction is probably rate controlling
during oxidation of the alloy at temperatures up to 650°C. The oxidation of
cupronickel alloy at temperatures less than 160°C produces a duplex oxide
structure /24/. The isochronal curves are found to pass through a maximum at
74% copper which is explained by diffusion of copper through a porous
nickel oxide structure extending through the metal consumption zone.
70 Brought to you by | Purdue University Libraries

Authenticated
Oxidation of copper-10 nickel and copper-24 nickel at 800°C produces

external scales consisting of a thick, inner C u 2 0 layer and a thin, outer CuO
layer, together with nickel rich internal oxide 1251. During annealing/
reoxidation in argon atmosphere the internal ( C u 2 0 ) oxides dissociate near
the oxide-alloy interface to give copper metal and oxygen.
The behaviour of cupronickel alloy in oxygen at 800°C /26/ was reported
and three types of distribution of NiO, C u 2 0 and CuO are illustrated on the
surface. The growth mechanism of the scales is discussed in terms of
competing fluxes of nickel atoms outwards and oxygen atoms inwards at the
alloy-oxide interface.
4. ELECTROCHEMICAL BEHAVIOUR O F
COPPER-NICKEL ALLOYS
The potential-pH diagram of 90/10 and 70/30 cupronickels in natural

seawater at ambient temperature has been derived by Efird 1211 and is given
in Fig. 2 (a & b).
The diagram defines the potential and pH region where these alloys are
immune or susceptible to various forms of corrosion in seawater; areas of
immunity, general corrosion, passivation and susceptibility to dealloying are
defined for each alloy. In the passivation region of the diagram for both the
alloys, C u 2 0 is formed directly on the sample surface as a passivating
species. In the general corrosion region of the diagram, dissolved species are
first formed and the corrosion product precipitates on the sample surface. The
corrosion rate rapidly decreases, probably due to surface enrichment in nickel
shifting surface composition to the passivation region of the diagrams.
90/10 cupronickel is immune to layer type dealloying in seawater, more
acidic than pH 8.5 at potentials more than -0.220V(SCE). 70/30 cupronickel
is immune to layer type dealloying in seawater more acidic than pH 7.8 at
potentials more active than -0.220V(SCE).
The magnetic and specific heat data of cupronickel alloy lead to the
conclusion that t h e ' d ' band of electronic energy levels for the alloy is filled
at 60 atomic percent copper and above. Passivity, should be a property of
alloys containing 40% and more of nickel. Pitting, result of passive-active
cells and biofouling data in seawater (restricted release of toxic anions by
passive alloys encourage fouling) as evidence of the passive state confirm
this predicted critical composition /4,28/.

71
Authenticated
An Overview
12
8 -
8
U
ÜJ Cu"
ο
ω
a ΰ 0 passivation -
>
Cu*
0 ω
LU
-u _ immunity
1 1 1 1 1 1 J 1 Γ"*
It
pH
12
ω Cu**
4 g
b LO 0 passivation (Λ
Cu*
ω
-U
mm unity
-8
-I 1 1 L J L—u
" " f 10 12
PH
Fig. 2: Pourbaix diagram of cupronickel alloys 1211.
The overall region where maximum pitting and biofouling occur is

evidence of the passive state (Fig. 3). T h e ' d ' band of the alloy, as indicated
by physical data, is filled at 60 atomic percent as or unfilled at 40 atomic

Authenticated
Fig. 3: Behaviour of cupronickel alloys in seawater/19/
percent nickel and above. Predicted minimum nickel content for passivity is
at 40 atomic percent or 38 wt.%.
5. C O R R O S I O N R E S I S T A N C E B E H A V I O U R O F
COPPER-NICKEL ALLOYS
Cupronickels are the most corrosion resistant of the commercial

copper alloys. Though the corrosion resistance of cupronickels is superior to
that of bronzes, the inherent disadvantage is the lack of corrosion resistance
under oxidising conditions. For example, in unaerated dilute HCl acid,
H3PO4, H 2 S 0 4 and organic acid, cupronickels show negligible corrosion, but
aerated acids and nitric acids corrode them badly. The chemical complexity
of the environment led to the corrosion performance of these alloys (Table. 2)
1291.
Corrosion behaviour is aggressive in polluted harbours and estuaries,
where the ebb and flow of tide cause twice daily changes from anoxic,
polluted brackish water to relatively fresh aerated seawater. In the latter
73
Authenticated
An Overview
Table.2
Typical corrosion rate (in ipy) of cupronickel alloys /29/
Environment 70/30 80/20 90/10

10% HCl 193
10%H2S04 19
38% HF 225
8.4% H3PO4 146 142 130
50% HNO3 — Highly corrosive—
10% acetic acid 5
INNH4OH 1.2
2N NaOH 0.0002
KOH 0.00002
10% N a 2 S 0 4 0.0033
10%NaN03 0.000013
IO%KNO3 0.000011
3 % NaCl 0.00034
sections, the corrosive properties of cupronickel alloys are reviewed

especially dealloying with the selected aggressive environments.
5.1 Atmospheric Corrosion

The nature of atmospheric corrosion, indoors and outdoors in a given
locality, very much depends upon local atmospheric pollution. If the number
of possible contaminants of the atmosphere is large, it is quite natural that the
performance of the alloy/material is poor. Thus, the tests run as per ASTM
(Table 3.) /30/ over a period of 10 years, in various types of atmospheres
reveal that the corrosion rates of the cupronickel alloys are very low and the
rates vary considerably from place to place. In a similar marine environment,
9 month exposure studies revealed that the 70/30 and 55/45 cupronickels
corroded at rates of 3.1 χ 10 s and 2.4 χ 10 s ipy respectively /31/.
The behaviour of cupronickels in sulphide atmosphere is the particular
interest of study, since copper alloys are subject to sulphidisation upon
exposure to the atmospheres and studied by many authors /32-36/. The
contents of nickel in the alloy are most important to the inhibition of
74
Authenticated
Table 3
Atmospheric corrosion of copper-nickel alloys /30/
Test site Corrosion rate in ipy

75copper, 20nickel, 70copper, 29nickel,
SZinc ITin
Industrial environment 8.55 χ 10" 5
7.96 χ ΙΟ-5
5
Marine atmosphere I 4.10 χ 10" 4.35 χ 10"5
Marine atmosphere II 1.17 χ 10"5 1.39 χ 10'5
Rural atmosphere I 1.38 χ 10'5 1.37 χ 10"5
6
Rural atmosphere I 3.50 χ 10" 3.00 χ 10"6
sulphidisation. Thus copper-10% nickel alloy sulphidised faster than

copper-50% nickel irrespective of the temperature. The rate of sulphidisation
decreases with increasing amount of cold work.
During sulphidisation the scales formed on the alloy surface consist of
several phases, each one essentially forming a discrete layer. The general
order of phase is alloy/nickel sulphide/copper sulphide and the proportion of
each sulphide varying with alloy composition. The scale mainly contains a
thin layer of Cu 2 S layer which decreases with increasing temperature,
essentially because of its decreasing thermodynamic stability. The degree to
which the surface oxide film inhibits copper diffusion is thus reflected in the
oxidation and sulphidisation behaviour of the alloy. The alloys containing at
least 10% of the alloying metals are some thirty times more resistant to
sulphidisation than pure copper.
5.2 Corrosion Behaviour in Aqueous Solutions

5.2.1. In chloride solutions
In neutral chloride media copper-nickel alloys 131-39/ electro-oxidised to
cuprous chloride complexes, whose rate is dependent on the chloride
concentration but independent of pH /40/. The electrodissolution rate is
strongly affected by the rate of mass transfer /41-42/. Dhar et al. /43/ studied
the corrosion of copper-nickel alloys in oxygenated 0.5M NaCl and in
synthetic seawater. In 0.5M NaCl, the corrosion proceeded through the
formation of a soluble CuCl2" complex. In synthetic seawater, the corrosion
proceeded through a surface kinetic process due to the formation of Cu 2 0 and
75
Authenticated
An Overview
CU2(OH)3C1 on the surface. Kato et al. /44/ studied in aerated 3.4 wt.% NaCl
solution at room temperature and found that the corrosion product layers on
the alloy surface thickened during the first 103 h.
North and Pryor /45/ observed reduced anodic and cathodic reaction rates
and suggested that these reductions are due to the increased anodic and
cathodic resistance during the formation of the layer. The decreased corrosion
rate was correlated with the defect structure of the corrosion product layers
/46-47/. The film formation on 90/10 alloy was dependent on applied current
and the relative concentrations of the ionic species H+, OH" and CI" in
solution /48/. The influence of corrosion product film formation has been
studied /49-50/ to elucidate the reason for the protective nature of these films.
In copper-nickel corrosion, oxygen reduction occurs at the bottom of pores in
the outer corrosion product layers and the corrosion rate is determined by the
diffusion of oxygen through the electrolyte to these sites.
Copper-nickel was believed to get its corrosion resistance from the inner
cuprous oxide layer /45,47/. Cuprous oxide has a cubic, copper deficient
lattice, making it a p-type semiconductor with low ionic resistance due to
highly mobile vacancies and low electronic resistance. The holes have low
activation energy for movement /51/. Addition of nickel and iron were
thought to improve the corrosion performance by substitution for copper in
the lattice, but this idea is not readily accepted in the context of the theory of
doping on substitutional transport in ionic solids.
The greater corrosion resistance of the copper-nickel alloys in aerated salt
water was due to a slower cathodic reaction, presumably oxygen reduction
/52/. The poor catalytic nature and/or poor electronic conductance of the
outer porous layer force oxygen to diffuse within the pore electrolyte to sites
deep in the porous layer. These deep sites may be of a catalytic nature and are
where electrons are readily available for reduction of the oxygen. The oxygen
diffusion step in the pore electrolyte partially or completely limits the rates
for the overall corrosion reaction.
Although an increase in nickel content was expected to improve the
resistance of copper-nickel alloys to localised corrosion, however the
behaviour of the particular alloy is strongly influenced by the chloride ion
concentration. For lower chloride concentration, an increase in nickel content
worsens the resistance to passive film breakdown, whereas for higher
chloride concentration an increase in the nickel content is beneficial.
Mansfeld and Uhlig /53-54/ explained the behaviour of nickel-copper
alloys through the electronic configuration theory of passivity. If t h e ' d ' shell
76
Authenticated
is unfilled, i.e. for copper content up to 40%, conditions favouring the

chemisorption of oxygen are established and stable passive films are formed.
Films formed on alloys containing more than 4 0 % copper, i.e. when the
critical atomic ratio of copper/nickel exceeds 1.6, are less stable.
As long as the nickel content in the alloy does not exceed 40%, passivity
in chloride solutions is established by the formation of an oxide film
consisting of an outer layer of cupric hydroxy chloride Cu 2 (OH) 3 CI,
overlaying a compact inner layer of C u 2 0 layer. This C u 2 0 layer is claimed
to be mainly responsible for the good corrosion resistance of copper-nickel
alloys. Due to its defective structure it can accept large amounts of foreign
ions, i.e. nickel or chloride ions. The composition of the reaction product is
strongly potential dependent and at more active potentials, where preference
for selective nickel dissolution is greater, the reaction product was found to
contain nickel concentration in excess of those in the alloy, e.g.
approximately 4 5 % at - 0 . 1 V for 70/30 alloy. At more positive potential, or
for longer polarisation times, nickel is preferentially dissolved from the
corrosion product due to its greater solubility in NaCl. The dissolution of
copper in the form of Cu 2 + ions results in the precipitation of an outer
Cu 2 (OH) 3 CI layer. In contrast to the inner C u 2 0 layer, the outer layer
contains little nickel.
The surface corrosion products formed on copper-nickel-iron alloy were
analysed 1551 and it was found to be a uniform, adherent protective film
containing FeOOH at the outside of the film. FeOOH promotes nickel
enrichment in the corrosion layer by preventing nickel from running off. But
without FeOOH the film was found to have a layered structure and was loose
and non-adherent. The effect of the addition of non-ionic surfactant /56/
shifted the pitting potentials of the copper-nickel alloys to more negative
values in alkaline chloride solution.
The surface layer (topmost layer) formed on 90/10 alloy was found to
contain nickel(ll) hydrated species and pronounced segregation of additive
alloying compounds. Metallic copper and nickel-based compounds were
homogeneously distributed within the segregants in the surface film.
Chauhan and Gadiyar 1511 found that the structure of the layer grown on
copper-nickel 90/10 alloy in synthetic seawater contains an outer C u 2 0 layer
with chemisorbed moisture and traces of chlorine, and an inner C u 2 0 layer
consisting of C u 2 0 and nickel ions in two different valency states i.e. Ni 2 +
and Ni 3 + . Nickel was predominantly present as N i 2 0 3 and therefore as Ni 3 + .

77
Authenticated
An Overview
5.2.2. In Acidic Solutions

Bockris et al. /58/ studied the electrodissolution of cupronickel alloys in
1.0N HCl with the electrolyte flowing at a velocity of 0.5 cmVs. They
obtained an anodic Tafel slope of 130 mV/decade for (90/10) copper-nickel
alloy and concluded that the overall dissolution reaction in this flow region
was charge-transfer controlled. Cahan and Hayer /59/ reported that Tafel
slopes for (30-90% Copper) copper-nickel alloys in 1.0N HCl are about 80
mV/decade and concluded that the overall reaction is controlled by the
dissolution of nickel. Walton and Brook /60-61/ investigated the electro-
chemical behaviour of (90/10) and (60/40) copper nickel alloys in 1/3 to 3 Μ
HCl acid at a sweep rate of 5 mV/sec. Two current plateaus and a current
minimum were observed for the 90/10 alloy. In the active region, cuprous
species were detected as the dissolution product, and at much higher
potentials, cupric species were found by means of a rotating ring disc
electrode.
Lee and Ken Nobe /62/ studied the electrodissolution of copper-nickel
alloys (with 1.7% Fe) in acid chloride solutions. Selective electrodissolution
of nickel in the apparent Tafel region and high rates of iron electrodissolution
were measured near the rest potential. The formation of a film consisting of
mainly CuCl was discerned to begin at about the peak potential. At higher
potentials where a current minimum and a current plateau were observed,
electrodissolution was non-selective and under mass-transfer control. In this
region, cuprous chloride complexes were the only electro-oxidation products
of the copper component. At potentials above the current plateau region, the
copper component electro-oxidised to cupric but under mixed activation and
mass-transfer control. In another study /63/, the electrodissolution kinetics of
95/5, 90/10 and 70/30 alloys in acid chloride solutions were found to be that
electrodissolution of copper component exhibited mixed mass transfer and
kinetic control in the apparent Tafel region and mass transfer control in the
limiting current region with cupric chloride complex indicated at the limiting
diffusion species. At potentials above the limiting diffusion current region,
formation of rate of cuprous and cupric species was under mass-transfer and
kinetic control, respectively. The effective thickness of the CuCl surface film
on the copper-nickel alloys decreased with increasing nickel content.
Ken Nobe and Bauerle /64/, reported the anodic dissolution of 90/10 and
70/30 in H 2 S 0 4 containing various concentrations of chloride ions. They
obtained an anodic Tafel slope of 40 mV/dec. and 70 mV/dec. for 90/10 alloy
without and with chloride (5 χ ΙΟ^Μ) in 0.5M H 2 S 0 4 . Similarly for 7 0 / 3 0 , 4 5

Authenticated
mV/dec. and 70 mV/dec. without and with chloride (3 χ 10"4M) addition.

They suggested that for the 90/10 and 70/30 copper-nickel alloys in acidic
chloride solutions, the electrooxidation products are CuCI2" and nickel(Il)
between the rest potential and current maximum. Electrooxidation of the
alloy to CuCl2" should be strongly influenced by mass transfer but
electrooxidation of nickel(II) should not.
Crundwell /65/ studied the anodic dissolution of 90/10 alloy in HCl acid
solutions and found that it was controlled by both mass transfer and reaction
in the apparent Tafel region. The kinetics of dissolution was similar to those
of pure copper for the partial currents due to the dissolution of both
copper-nickel components from the alloy. The dissolution was controlled by
the dissolution of the copper from the alloy. In the limiting-current region a
film of CuCl precipitated on the surface of the electrode. Mass transfer
controlled the reaction in the limiting-current region. A mechanism which
described the precipitation and dissolution of the film and the diffusion of the
chloride to the surface of the electrode was proposed.
Mishra and Burstein /66/ studied the behaviour of copper-nickel alloys in
1M H 2 S0 4 and reported that at low potentials a monolayer of film grew
which was designated as MOH (M = Copper + or Nickef). The kinetics of
formation of the monolayer follows Tafel's equation. At higher potentials the
passivation of the metals occurred by film growth under high electric field.
The rate of film growth for all metals was controlled largely by nickel oxide
component of the film.
The passive layer formed in acidic electrolyte (phthalate buffer pH 5.0
and 0.005M H 2 S0 4 + 0.995 Μ K 2 S0 4 pH 2) revealed 1611, the corrosion
behaviour of cupronickels was characterised by the characteristic properties
of both alloy components, i.e. increased dissolution of copper and passivating
properties of nickel in acidic electrolytes. A similar multilayer structure with
an outer hydroxide and an inner oxide with lower valent cations in an inner
portion were found copper for alkaline solutions. The incorporation of copper
ions in the outer hydroxide part was extremely small and approached zero for
low pH as a consequence of the increased dissolution rate of Cu 2+ for acidic
electrolytes.
5.2.3. In Alkaline Solutions

The behaviour of copper-nickel alloys in slightly alkaline solutions
containing chloride ions has been extensively studied /68-71/ and the general
composition of the passive layer can be described by an outer CuO/Cu(OH) 2
Brought to you by | Purdue University Libraries 79

Authenticated
An Overview
layer overlying a Cu 2 0 barrier layer, which contained incorporated nickel

cations. The surface passive layers formed on copper-nickel in 1M NaOH
were found to contain /72-74/ First a Ni(OH) 2 layer. The rapidly growing
Ni(OH) 2 led to an accumulation of copper at the metal surface, which caused
the formation of an oxide underneath consisting mainly CuO. At more
positive potentials NiO entered the oxide sublayers. Cu 2 0 appeared to a
minor extent at the metal/oxide interface during the initial stages of CuO
formation and was no longer detected when CuO grew to a larger thickness at
sufficiently positive potentials. In the potential range of the beginning
transpassive behaviour the top Ni(OH) 2 layer was oxidised to NiOOH.
Parallel to the NiOOH formation Cu(OH) 2 was incorporated into the
hydroxide overlay er.
5.3 Corrosion in Marine Environment

Copper-nickel alloys are employed almost exclusively for piping in all
ships, heat changers piping in many commercial ships and power plants
cooled by seawater. Since cupronickels can develop corrosion product films
that become sufficiently protective over a period of time to reduce the rate of
release of copper in corrosion products below the critical limit 1151. The role
of this film in reducing corrosion is controversial since the behaviour is
greatly affected by oxygen content, velocity, temperature, pollutants and
biological organisms. Several studies /76-94/ have addressed the problem of
accelerated corrosion in marine/seawater environments. Much of this was
stimulated by reports that copper-nickel alloy piping prematurely failed on
naval ships in a polluted estuary water 1951.
5.3.1. Effect of oxygen content

The prime source for the corrosion of cupronickels is the dissolved
oxygen which is the normal oxidant present in the environment. In unpolluted
deaerated seawater, the corrosion rates were extremely low because cathodic
reaction was limited to the reduction of the trace amounts of dissolved
oxygen present /96/. In deaerated seawater (dissolved oxygen content ~ 0.045
mg/dm 3 ), the corrosion potential was always more than -0.3 V Vs SCE,
oxygen reduction was the only possible cathodic reaction and the corrosion
rates were low /97/. 70/30 cupronickel alloy exhibited superior corrosion
resistance to the 90/10 cupronickel alloy over the exposure times employed,
if oxygen concentration is maintained at or beneath the air saturated value of

Authenticated
6.60 mg/L. The corrosion reaction was cathodically controlled at low oxygen
concentrations, but was anodically controlled at high concentrations. At
higher oxygen concentration ( [ 0 2 ] = 26.3 mg/L), no difference between the
high and low nickel alloys was apparent. It was explained that the loss in
corrosion resistance of the 70/30 cupronickel alloy was due to a shift in the
corrosion potential to a value that was more noble than the potential at which
large anodic currents were observed when the potential was swept in the
active to noble direction.
The principal corrosion product due to the oxygen attack was found to be
C u 2 0 . This may be formed by the direct complexing of copper by chloride
according to the following reaction /27/ and CuCl 2 ' is a dissolved species in
the presence of chloride,
Cu + 2C1 — CuCl 2 " + e'
The solid C u 2 0 then forms by hydrolysis of the CuCl 2 " complex,
CUCI 2 " + H 2 0 C u 2 0 + 4C1" + 2 H +
This reaction is autocatalytic with respect to copper and also resulted in

the acidification of the solution immediately adjacent to the surface. To
control the biological activity of metal surfaces, ozone was used in the heat
exchanger system /98/. The usage of ozone enhanced the oxygen content in
the environment. The effect of ozone on the corrosion behaviour of 70/30
resulted in a noble shift in the corrosion potential. The shift was virtually
instantaneous in contrast to a significant transient period to achieve a
steady-state potential in solutions that did not contain ozone. The corrosion
potential in ozonated solutions was almost independent of concentrations in
presence of dissolved ozone for 70/30 cupronickel, resulted in a thinner film
containing a higher fraction of oxygen to chloride than for unozonated
solutions. Reduction of ozone occurred and resulted in the increase in oxygen
concentration.
0 3 + 2 H + + 2E -> 0 2 + H20
Thus, the hydrolysis reaction is enhanced because of the availability of

oxygen,
Brought to you by | Purdue University Libraries 81

Authenticated
An Overview
4CUC12" + H 2 0 + V2O2 -> 2Cu 2 0 + 8C1" + 2H+
The hypothesized reaction can explain the shift in the corrosion potential
in the noble direction and supports the thinner, apparently more protective
corrosion product film formation.
5.3.2. Effect of temperature

Temperature exercises a strong influence on the corrosion behaviour of
cupronickel alloys. In aqueous solutions, a temperature rise of the corroding
solution of about 20°C will approximately double the rate of corrosion in 3%
sodium chloride solution. This relation appears to hold true in the
temperature range of 0° to 75°C. Ijsseling et al. reported that the rate of
corrosion of a copper-10%nickel-1.4%iron alloy in aerated seawater at
40-50°C at the sea surface was lower than at 10-30°C and greater depths 1991.
This is primarily because of the quicker formation and better adherence of the
protective corrosion product layer formed at the higher temperatures. Stewart
and LaQue reported that the 70/30 and 90/10 alloy retained good resistance to
corrosion by seawater at temperatures well above normal i.e., at 162°C. These
results confirmed the ability of the alloy to withstand impingement attack by
seawater at temperatures higher than normal. In a similar work, the results for
70/30 cupronickel containing Fe explained the poor resistance to
impingement attack at low temperature greater than 10°C /100/. At
temperature below 10°C the potential of the 70/30 alloy remained more or
less constant at about -200mV (SCE). This may be due to an enrichment of
iron in the film of 70/30 cupronickel alloy. The corrosion rates of 70/30 and
90/10 cupronickels were found to be lower at 101°C than at 50° to 77°C;
however a minimum 60 day exposure is required to form a protective film
and establish long time attack rates /101 /.
Detailed investigations /102-104/ carried out for 70/30 alloy in seawater
at different temperatures (20,40, 60, 80°C) revealed that (a) the corrosion rate
of the alloy increases, (b) selective copper dissolution takes place, and (c) the
nickel amount in the corrosion products increases owing to the formation of
copper-nickel oxide with a nickel content higher than in the alloy. At 80cC,
the kinetics of the dissolution process of 70/30 alloy was governed by a
transport-limited mechanism. The corrosion process was under cathodic
control and the reduction of dissolved oxygen was the most important
parameter of the corrosion process. The surface studies emphasised that
composition of the passive films changed with the exposure time. Main

Authenticated
components of the passive film formed on the metal surfaces were nickel
compounds after a short exposure time and copper compounds after a long
exposure time.
Another attempt /105/, was made to correlate the variations in
microstructure and iron content with the formation of protective corrosion
product layers at low temperature ranges (LTR) (20 to 40°C). Here LTR is
intended to cover the temperatures at which condensers and pipelines usually
operates. Temperature has a significant influence on the film formation
characteristics mainly for the homogenised and continuous precipitation
alloys. At 40°C, good protective corrosion product layers were formed
rapidly with in a short time of exposure. Such corrosion product layers
produced a characteristic maximum in the free corrosion potential versus
time of exposure curve. The corrosion product films were thin and adhered
well.
In contrast, at 20°C thicker more porous films were obtained, which did
not give adequate protection for exposure time up to 250 hours. The same
behaviour was observed for the discontinuous precipitate alloy, at both 20
and 40°C. The rapidly formed and protective corrosion product layers
obtained at 40°C exhibit 'p' type semiconducting properties. Another type of
attack coming from temperature is known as 'hot spot' corrosion /106/, due
to thermogalvanic effects. This localised attack occurs on the cooling side of
the tube opposite a local high temperature area on the steam side. 90/10
CuNiFe alloy is much less prone to this type of attack.
5.3.3. Effect of velocity

Localised corrosion of the cupronickel alloys occurred at those points
where the corrosive liquid was in motion, such as in tube and pipe bends
screens and in areas where the cross-sectional area of the piping system was
suddenly reduced. When another phase was present in the fluid stream, such
as sand, various debris, and gas bubbles, the effect of velocity became more
serious. The addition of iron in the alloys considerably improved their
impingement and general corrosion resistance. Under service conditions,
appreciable differences in the performance of the cupronickel alloys have
been encountered /107-110/. The 70/30 alloy containing not less then 0.5%
iron withstood operational water speeds of over 15ft/sec and in conditions of
non turbulent flow nearly twice that speed may be restricted /111/. Heat
exchangers run at such low speeds that sludge carried into the system settles
in the tubes encouraging over heating. A porous oxygen shield on the metal

83
Authenticated
An Overview
surface encouraged 'shielded area attack' under the debris. Therefore, it is

strongly recommended that i f the slow running o f a condenser exceeds more
than a very short period o f time the component should be flushed through
with clean water at the earliest opportunity.
The effect o f velocity on cupronickel alloys was studied by Stewart et al.
I M I. A continuous flow o f clean sea water at a velocity o f 2 ft/sec. revealed
maximum corrosion resistance by the alloys that contained 0 . 8 % or more
iron. The 70/30 which contained 0 . 0 5 % Fe was carried three times as fast
(12mdd) as the 90/10 alloy with 0 . 8 % F e . 70/30 which contained 0 . 5 % F e was
corroded at half the rate - 2mdd. None o f these alloys suffered any
significant pitting under these conditions o f exposure.
In similar tests but at high velocity (jet impingement tests), 90/10 which
contained 0.7 or 2 % Fe demonstrated good resistance to impingement attack.
The resistance o f 90/10 alloy was much better than 70/30 o f low iron content
and was equal to 70/30 with high iron content. Thus, in 90/10 as the iron
content increased, the resistance to impingement attack also increased. In
another flow velocity study /112/ o f 90/10 & 70/30 cupronickel alloys at
seawater velocities up to 5 m/sec. (Reynolds number 7 4 , 0 0 0 ) , the corrosion
rates in the sulphide polluted seawater were lower than in aerated seawater.
In aerated seawater, the high nickel alloy suffered localised corrosion at 3
m/sec and higher velocities. The rate o f localised corrosion was high and
became more intense as the velocity was increased from 3 to 5 m/sec. The
filmed surfaces were generally nobler than unfllmed surface. High flow
velocities caused removal or prevented the formation o f corrosion product
films. This development o f differences in potential between filmed and
unfilmed surfaces led to considerable acceleration o f corrosion o f unfllmed
areas adjacent to filmed surfaces. High velocities were likely to be more
damaging than low velocities primarily because they presented greater
velocity gradients to become established. The suggested limiting design
velocities for cupronickels in seawater piping system are given in Table 4.
/II3/. The 95%copper-5%nickel alloy has been used for seawater carrying
pipes under conditions o f non-turbulent flow it withstood an average speeds
o f 5.7 ft/sec. The suggested critical velocity limits for condenser tube alloys,
for 90/10 alloy is 10 ft/sec. and for 70/30 alloy is 12 ft/sec.
5.3.4. Effect of pollutants

The seawater is a complex chemical system affected by contamination.
Various pollutants are often introduced in seawater by wet and dry deposition

Authenticated
Table.4
Limiting design velocities (ft/sec.) /113/
Alloy Pipe sizes

Under 3 in. 4 to 10 in. O v e r 10 in.
90/10 8 10 12
70/30 10 12 15
and by improper dumping of municipal wastewater. These pollutants often

affect the corrosivity of seawater on copper-based alloys, which might be
thought to be highly resistant in the marine environments. Several studies
/114-118/ have addressed the problem of accelerated corrosion of cupronickel
alloys in polluted environments. Alhajji et al. /119-122/ monitored the
corrosion characteristics of 90/10 and 70/30 cupronickels in the presence of
some common pollutants such as urea, sodium sulphite, sodium nitrate,
sodium phosphate, copper sulphate, lead acetate, a m m o n i u m sulphate and
ammonium chloride in the presence and absence of sulphide and found that
the ammonia and sulphide based compounds are the worst pollutants which
greatly affect the corrosion resistant behaviour of cupronickels.
5.3.4.1. Sulphide pollution

Copper alloys suffer accelerated corrosion when they are exposed to
seawater polluted with sulphides. Several surveys and reports /123-134/
document the adverse effect of dissolved sulphide on copper alloy tubing and
piping in service situations. A m o n g the principal sources of sulphide in
seawater /135/ are the action of sulphate reducing bacteria under anoxic
(oxygen free) conditions on the natural sulphate content of the seawater, and
putrefaction of organic sulphur compounds (proteins, etc.) from sanitary or
industrial sewage.
Bates and Popplewell /136/ investigated the corrosion of 90/10 and 70/30
cupronickels in flowing (2.1 and 1.4 m/sec) aerated synthetic seawater with
addition of sulphide from sodium sulphide. 90/10 showed slight inlet erosion
and superficial pitting whereas 70/30 showed heavy weight loss associated
with severe surface roughening as well as slight pitting and colour change
characteristic of superficial dealloying . The higher corrosion rates are due to
a highly defective C u 2 0 containing Cu 2 S which permits rapid ionic and
electronic transport through it.
Brought to you by | Purdue University Libraries85

Authenticated
An Overview
Gudas and Hack /137/ monitored the corrosion rates of 90/10 cupronickel
and compared corrosion rates obtained in control tests in unpolluted seawater
with those in the polluted environments. The latter were much higher and in
most instances, remained high even long after sulphide additions had been
terminated. The effects of dissolved sulphide content /138-139/, seawater
velocity /112,140/ and the oxidation of the dissolved sulphide by oxygen
/140,141/ have been studied for both 90/10 and 70/30 cupronickel alloys in
natural seawater. Slight changes in the test conditions could have led to quite
different results.
In determining the effect of sulphide, Macdonald et al. /138,139/
monitored the corrosion rates of the cupronickel alloys in deaerated seawater
containing 0-55g/m 3 sulphide flowing at 1.62 m/sec. In unpolluted deaerated
seawater, the corrosion rates were extremely low because the cathodic
reaction was limited to the reduction of the trace amounts of dissolved
oxygen present. In sulphide polluted de-aerated seawater, corrosion rates
were much higher. This is because an active shift in the corrosion potential
occurred by hydrogen ion reduction. Thus the rate and nature of corrosion in
sulphide contaminated brine is strongly dependent upon the degree of
aeration in the seawater, and the aerated sulphide being very aggressive.
It would appear that an accelerated attack is not caused by the presence of
sulphide alone, even at high sulphide contents or under adverse flow
conditions. Laboratory experiments, performed under controlled conditions
have shown that dissolved oxygen plays a critical role in the accelerated,
sulphide-induced corrosion of cupronickel alloys /140-141/. It is possible that
the dissolved sulphide was homogeneously oxidised by the dissolved oxygen
to produce species that were particularly corrosive towards copper alloys.
The accelerated attack of copper-nickel alloys could then result from contact
with these sulphide oxidation products rather than with the sulphide or
oxygen from which they were derived.
In considering the synergism between dissolved oxygen and sulphide,
Syrett et al. /142/ performed experiments in seawater containing oxygen,
sulphide, sulphur and polysulphide either singly or in combination. These
experiments demonstrated that sulphur or polysulphides were just as effective
as sulphide in promoting corrosion in de-aerated seawater, but that compared
with oxygen, none of the sulphur-containing species caused a dramatic
increase in the corrosion rate. The presence of the sulphur species did have a
profound effect on the character of the surface film. The cuprous oxide Films
formed during the one-day exposure to unpolluted seawater were relatively

Authenticated
smooth and nonporous, while the pre-exposure to sulphide resulted in the

formation of a porous, non-protective, cuprous sulphide film on the
cupronickel alloy surface. It was speculated that the presence of dissolved
sulphide (or sulphide oxidation products) does not lead directly to accelerated
corrosion but the porous cuprous sulphide corrosion product formed in the
polluted water interfered with the normal growth of the protective oxide film
/143/. Thus, in sulphide polluted environment, the film formed was a mixture
of Cu 2 0 and Cu 2 S. Under sulphide polluted environment the stress corrosion
cracking of 90/10 and 70/30 cupronickel alloy were reported /144-147/ under
the slow strain rate conditions in conc. 0.1-1 Μ sulphide solutions. The
mechanism of cracking is attributed to a dealloying or selective dissolution
phenomenon where the copper matrix but not the solute nickel is selectively
removed. In a dealloying phenomenon of 70/30-cupronickel alloy in low
sulphide polluted seawater the mean corrosion resistance of the alloy
increased and slightly copper dissolution took place. In highly polluted
seawater, the corrosion resistance decreased while slightly selective nickel
dissolution took place.
Hack and Gudas /148/ and Eiselstein et al. /149/ have shown that very
high rates of corrosion occurred during simultaneous exposure to sulphide
and oxygen. In deaerated solutions /150/, the effect of addition of sulphide
increased the kinetics of the anodic reaction, since it changed from cuprous
oxide formation in the sulphide-free solution to cuprous sulphide formation
in the sulphide-polluted solution. Oxygen-reduction was not the cathodic
reaction and the corrosion potential shifted in the less noble direction with
sulphide addition.
The corrosion products on 90/10 copper-nickel alloy in sulphide
environment were found to be Cu2S and CU2(OH)3C1 and they consisted of
outer porous layers and thin inner adherent layers /151/. These corrosion
products were much thicker (times) than those developed in sulphide free
solutions /44/. This high corrosion rate, which matched or exceeded that of
service failures, was attributed to the much-increased catalytic nature of the
porous corrosion products for the oxygen-reduction reaction when they
contain sulphide. The surface film formed on cupronickel alloys in seawater
containing various concentration of dissolved oxygen and dissolved sulphide
was found to contain chalconite, paratoamite, cuprite, aragonite and possible
djurleite and digenite on the surface /152/. This film composition varied with
solution chemistry.
87
Authenticated
An Overview
5.3.4.2. Ammonia pollution

A m m o n i a is another possible corrosion pollutant for copper alloys in
marine environments. Laboratory tests /153/ showed that 10 ppm of NH 4 +
were effective in causing pitting corrosion but were not as aggressive as
hydrogen sulphide. The stress corrosion cracking resistance of 90/10 alloy in
a moist ammonia atmosphere has been found to be considerably improved by
the addition of Fe /154/. The addition of iron was found to be most beneficial
and 1.5 w t % Fe imparted complete immunity to stress corrosion cracking
after 1000h of testing.
Ahmed and Abdul Allem /155/ investigated the corrosion behaviour of
90/10 cupronickel in Arabian Gulf water containing N H 4 O H 80-800 mg/1.
The alloy had higher corrosion resistance in deaerated water than aerated
water. For corrosion free performance, the upper level of N H 4 O H is 800 mg/1
or 10 2 M for the Re No. 6.0 χ 104. Schiffrin and De Sanchez /156/, explained
that the influence of the NH 4 + ion is less apparent. It was thought that this
was a likely pollutant in contaminated seawater, but only a slight increase in
the cathodic reaction rate was actually observed. Although NH 3 was a good
ligand for copper ions, no significant enhancement of the anodic reaction was
detected, and it is unlikely that the presence of this ions played a significant
role in the enhancement of flow corrosion by contaminated seawater (at least
at the low concentration levels studied).
The independence of the anodic reaction rate from NH 4 + ion addition was
rationalised by considering the solution equilibrium properties of cuprous
co-ordination compounds. The equilibrium constants for the formation of
CuCI 2 - and Cu(NH 3 ) 2 + ions are K 2 C1 = 3.2 χ 105 and K 2 ( N H 3 ) = 5.5 χ 108,
respectively, where K 2 is the equilibrium constant referred to the formation of
the complex. The ammonia complex is more stable; the ratio of concentration
of CI' and N H 3 does not favour the formation of Cu(NH 3 ) 2 + . The free
ammonia concentration in pH 8 seawater containing lOppm of NH 4 + ion is
3.2 χ 10"5M. The chloride ion concentration in the seawater is 0.53 M. For a
10 ppm NH 4 + ion contamination, the ratio of concentrations of the two
complexes if [CuCl 2 "]/[ Cu(NH 3 ) 2 + ] = 1.6 χ 105 and therefore, the chemical
steps for the anodic process were not altered by low level contamination with
NH 4 + . Rajagopalan et al. /157/ carried out corrosion tests of 70/30 and 90/10
alloys in contaminated seawater with 1 ppm of NH 3 or more, and emphasised
that N H 3 has only a slight effect in increasing the rate of corrosion of 90/10
and has no observable effect on the behaviour of 70/30 cupronickel alloy.
Giuliani et al. and Francis /113,114/ also found the effect of ammonia

Authenticated
concentration on the corrosion resistance behaviour of cupronickels.

Corrosion fatigue experiments /158/ with cupronickel 70/30 alloy in an
NH4OH environment report that the decrease in fatigue strength was similar
to their property to SCC. The amount of intergranular fracture was
proportional to the decrease in the fatigue strength. The fracture morphology
changed from a transgranular to an inter granular mode.
5.4 Effect of Fouling and Microbial Corrosion

A solid surface in contact with seawater rapidly becomes covered with
organic nutrients, which enhance bacterial activity /159/ and eventually lead
to the formation of primary films /160-162/. It is important to recognise the
existence of different phases of bacterial attachment /156/. The first stage
probably involves different layer interactions and dispersive interaction
energies between the solid/solution and bacteria/solution interfaces. The
second attachment phase causes irreversible polymeric bridging of the
bacterial surface to the solid, thus permitting colonization. During this second
phase, the bacterial colonises for extracellular polymers, mainly
polysaccharides, which act as attachment and bacterial colony support media.
The bacteria and other organisms that grow on this slime film are not easily
dislodged from the surface and can withstand high hydrodynamic regimes
such as seawater flow rates of 1.8 m/sec.
Bacterial contamination produces a variety of phenomena, the most
important of which is the colonization of the metal surface by Cu + + resistant
species /156/. Of these, the genus Pseudomonas appears to be the most
aggressive and causes a long-term enhancement of the corrosion rate of 5 to
10 times that of a mixed culture. For enhancement of corrosion rate, the
possibility of two different modes of action should be considered.
1. The homogeneous generation of metabolites than can be act as efficient

cathodic depolarizes and
2. The creation of a surface chemical microenvironment produced by the
formation of slimes that hinder the diffusion processes and depassivate
the metal.
Besides the acceleration in the rate of uniform corrosion, differential

aeration may produce localised effects. The formation of sulphide ions as a
consequence of protein degradation can lead to the acceleration of the
89
Authenticated
An Overview
cathodic corrosion reaction despite the instability of the sulphide ions in

aerated seawater.
The problems of aerobic bacterial contamination are compounded by the
possibility of rapid activation of the sulphate reducing bacteria(SRB) if local
anaerobic conditions are established, and materials operating with
contaminated seawater are subject to attack by a combination of bacterial and
sulphide ion effects. For a completely fouled surface, the local environment
created by the colonies will determine the corrosion behaviour since diffusion
and transport of metabolites will be significantly hindered.
Corrosion resistance of cupronickels is due to the formation of passive
surface films when exposed to seawater. Therefore it is not surprising that
failure is always associated with the deterioration of the protective film.
Apart from the marine pollutants, the bacterial microfouling has a significant
role in the deterioration of the surface films formed on cupronickels.
Studies /163-166/ on the effect of biofilm formation at early stages on the
corrosion behaviour of 70/30 alloy revealed that the protective characteristics
of the complex layers formation on the alloy surface were found to be altered
by microbial adhesion to the metal surface. Although the antifouling property
is well documented, the protective characteristics of the complex layers that
are formed on their surfaces could be distorted by the action of
microorganisms. The incorporation of biological material close to the metal
surface caused oxygen removal and affected cathodic reaction control. The
production of exo polymeric substances by the microorganisms modified the
transport properties at the metal/solution interface generating diffusional
barriers. A loose structure of the outer layer of corrosion products was
obtained when biofilms were present at the metal/solution interface. Under
these conditions the sloughing off of the protective layers enhanced the risk
of localised corrosion at restricted sites of the metal surface.
High levels of organic materials in polluted seawater facilitated bacterial
adherence to toxic surfaces such as cupronickels /167/. Some stalked
microorganisms attached strongly to cupronickel surfaces and were able to
cause the partial detachment of the outer layers of corrosion products.
Sulphide anions can enhance chloride anion effect on copper-nickel
dissolution, m o d i f y the structure of passive layers by facilitating the initiation
of localised attack. This situation can be found in the vicinity of SRB
colonies or under microbial consortia. Surface inhomogeneity can enhance
the partial detachment of passive films leading to differential aeration effects.
It has been reported /168/ that sulphate reducing bacteria (SRB) are able
90
Authenticated
to produce significant concentrations of sulphides in highly restricted areas of

both 90/10 /169/ and 70/30 /170/ cupronickel alloys. SRB are able to survive
on cupronickel surfaces in spite of considerable percentages of oxygen at the
metal/solution interface /171/. The corrosion hazard is greater in these
conditions, because of the high local concentration of sulphide that can be
produced under microbial consortia of SRB and other heterotrophic bacteria
/172/.
Vedela et al. /173/ in their studies revealed that the 70/30 alloy surface
exhibited delayed and reduced microfouling settlements together with less
species diversity due, presumably, to the high copper concentrations. On the
other hand, organic adsorption may occur in 70/30 facilitating the attachment
of biological species. Another important effect of extracellular organic
substances is related to their enhancement of corrosion /174/. The acidic
exopolymers produced by sessile, biofilm forming bacteria have the capacity
to corrode a copper surface.
Mansfeld and Little /175/ reported that copper surfaces exposed to natural
seawater were colonised by bacteria within 3 weeks of exposure independent
of alloy composition. The corrosion rates were higher in natural seawater
when compared to artificial seawater. Intergranular corrosion and denickeli-
fication of 70/30 alloys were reported after one-month exposure.
Little et al. /176/ and Wagner /177/ reported that the localised corrosion
due to microbial induced corrosion was due to the metal segregation during
welding process, settlement of sulphide producing bacteria in welds,
disruption of surface films by turbulence and formation of adjacent cathodic
and anodic areas.
The cupronickel, having inherent biofouling resistance in seawater,
suppresses the dense film formation on its surface /178-180/ as revealed in
our exposure studies in Tuticorin harbour waters / 181-182/. The cupronickel
surface was found to be fouling freely even after an exposure period of one
year. Exposure of 90/10 alloy to Antarctic marine waters was reported by
Maki et al. /183/. During the first 2 hours, cupronickels accumulated with
more pyrolysable organisms. No significant increase of attachment of
bacteria and process controlling bacteria adhesion were observed on
cupronickels. Intergranular corrosion was reported /184/ for 70/30
cupronickel alloy under elliptical deposits of embedded diatoms. Dealloying
and intergranular attack did not occur in artificial seawater. Sulphides
produces by bacteria have accelerated attack of nickel in grain boundaries of
70/30 alloy.
91
Authenticated
An Overview
6. PREVENTIVE OR REMEDIAL MEASURES
There are several methods available to control the corrosion of

cupronickel alloys. Among these, 1) the use of inhibitors, 2) flushing the
systems involved with clean fresh water 3) cathodic protection /185/ are the
various ways reported in decreasing the corrosion rate of cupronickel alloys.
The protective action of iron for copper-nickel alloys and the treatment of
condenser tubes (CuNi alloy) with ferrous sulphate has proved quite effective
in preventing corrosion and erosion of these alloy materials is well
documented /186-191/. At low levels of sulphide contaminant, intermittent
ferrous sulphate dosage was effective, but at higher levels, continuous
injection was necessary.
During the treatment involving FeS0 4 to corrosive saline waters, the
protective action of iron in corrosion products is well documented. There are
two possible mechanisms /192/ for the protective action of iron are,
1. The deposition of a brown layer of lepidocrocite (γ - FeOOH) on the

cathodic areas of the metal surface. These increase the polarisation of the
cathodic reaction which is believed to be the reduction of dissolved
oxygen. Ferrous ions in solution are oxidised directly to lepidocrocite as
follows:
2Fe ++ + 4 0 H - + Ά 02 -> 2FeO.OH + H 2 0
the lepidocrocite is then carried electrophoretically to the cathode areas.
2. Formation of a film of partially hydrated Fe 2 0 3 that causes a substantial

increase of the cathodic polarisation and reduces the loss in weight due to
erosion and consequently the formation of new anodic areas.
Rowlands /193/ investigated the use of sodium dimethyl dithiocarbamate

(SDD) as corrosion inhibitors for copper-nickel pipe and tube. The SDD
forms an insoluble copper-chelate film on the metal surface thus reducing
corrosion. The effect of benzotriazole (BTA) was investigated /194-195/ as a
corrosion inhibitor for copper alloys and it was found that BTA forms a
copper (I) BTA surface complex. For copper-nickel alloys the time taken to
form Copper (I) BTA film is dependent on the alloy composition. The
adsorption of BTA on cathodically reduced copper surfaces strongly supports
92
Authenticated
previous suggestions that the presence of C u 2 0 facilitates formation of the

surface films. The effect of BTA altered the dynamics of the film formation
and dissolution processes and resulted in morphological changes on the metal
surface. The sodium dichromate (Na 2 Cr 2 0 7 ) /196/ pretreatment has proven to
be most consistent in reducing initial corrosion rates and has been shown
beneficial in reducing longer-term corrosion rates in seawater. Additionally,
it does not appear to impair other properties such as biofouling resistance and
erosion-corrosion resistance. The effect of Chromate addition (0.25 to 1 ppm)
as corrosion inhibitor have been tested in flowing 110 to 121°C seawater and
the corrosion rate was found to be 0.036 to 0.15 mpy /197/.
The effect of sodium salt of 1-hydroxy e t h a n e - l , l - d i phosphonic acid
/198/ as inhibitor for C u N i l O F e l M n in cooling water has been evaluated and
it was found that 100 ppm HEDP decreased the corrosion rate in presence of
Zn 2 + ions. Highly alkyl benzotriazoles have been studied /199/ as corrosion
inhibitors of copper alloys in aqueous systems. Thus alkoxybenztriazole in
combination with another azole /200/ in the weight ratio of 0.01:100 to 1:100
was found to be an effective corrosion inhibitor for the copper alloys. The
corrosion of copper and copper alloys /201/ in sulphide containing water is
prevented by treating the water with > 0.1 ppm of Zn 2 + preferably complexed
with anionic water-soluble co-polymer having a low molecular weight
(acrylic acid-acrylate type co-polymers). Corrosion of copper alloys could be
avoided by adding an azole and a chelating agent (butyl benzotriazole and
tetra sodium EDTA) at 0.1 to 1000 ppm each /202/. Polyphosphate and an
azole /203/ at 50:1 to 1:50 weight ratio (azole is selected from C 2 .i2-alkyl - or
alkoxy benztriazoles, toly triazole, benztriazole, mercaptobenzotriazole and
l-phenyl-5-mercapto tetrazole, the polyphosphate is optionally phosphorylate
polyol) is suitable for protection of copper alloys as a corrosion inhibitor.
Reda et al. /204/ investigated the effect of organic complexing agent such
as fuchsin in the concentration of 5 ppm as an excellent inhibitor for 70/30 in
sulphide polluted seawater. Another metal complexing agent, SSA
(5-sulphosalicylic acid), was effective for the 90/10 in sulphide polluted
seawater while it was ineffective for 70/30 cupronickel alloy. EDTA di-
sodium salt was effective for both copper-nickel alloys. The addition of
anionic surfactant /205/ SDS inhibited the corrosion of copper-nickel alloy
under certain conditions of pH and surfactant concentration but cationic
surfactant CTAB enhanced corrosion. Formaldehyde reduced the corrosion in
slightly acidic solution. Gasparini et al. 12061 also proposed a mechanism in
which deposition of negatively charged particles of lepidocrocite over the
93
Authenticated
An Overview
Cu 2 0 film formed initially on the tube surface. The electric field associated
with the Cu 2 0 film, which had a zeta potential, extended into the bulk of the
solution at the operating flow rates, attracting the lepidocrocite particles and
causing those that reach the surface to adhere to it. The existence of a
spontaneous cathode (positive zeta potential) associated with the Cu 2 0 film
further favoured the deposition of negative lepidocrocite particles.
It was reported /207/ that the corrosion of cupronickel alloys in sulphide
polluted environment may be avoided by using a stimulated iron anode.
Ferrous ion from a simulated iron anode system were also effective in
eliminating or reducing sulphide induced corrosion of the cupronickel alloys.
7. CONCLUSIONS
The copper nickel alloys exhibit good corrosion resistance to pitting and
erosion corrosion in seawater applications. With up to 40% nickel in the alloy
corrosion resistance increased and remained constant afterwards. Oxidation
of these alloys exhibits interesting features. At temperatures less than 160°C,
they produce duplex oxide structure. At 800°C they produce scales consisting
of a thick, inner Cu 2 0 and a thin outer CuO layer together with nickel
internal oxide. In non-oxidising environments they offer better corrosion
resistance than bronzes. In sulphide atmospheres, sulphidization occurs and
the surface layer composition varies with alloy composition. The general
order is alloy/nickel sulphide/CuS. In chloride solutions they undergo pitting.
Increase in nickel content in the alloy plays a crucial role towards pitting. For
lower chloride concentration, the high nickel alloy destroys passivation and
at higher chloride concentration the alloys are corrosion resistant. In alkaline
solutions, the passive layers formed on these alloys have an outer
CUO/CU(OH)2 layer overlaying a Cu 2 0 barrier layer with nickel cations
incorporated. In seawater the corrosion of these alloys is due to dissolved
oxygen and temperature plays a crucial role. Localised attack occurred in
spots where the liquid is motion. High flow velocities of seawater caused the
removal or prevented the formation of corrosion product film. Cupronickel
alloys undergo severe corrosion in seawater polluted by sulphide and
ammonia. The passive films formed on cupronickels are destroyed by the
presence of microorganisms present in seawater. Sulphides produced by the
bacteria accelerated the corrosion.

Authenticated
Corrosion control of these alloys was effectively carried out by the use of
inhibitors in the medium, applying cathodic protection and addition of a less
noble element in the cupronickel alloy.
Cupronickel alloys are still extensively used for marine applications and
seagoing vessels still employ these work horses in their heat exchangers.
ACKNOWLEDGEMENT
One of the authors, J. Mathiyarasu, expresses his sincere thanks to CSIR,

New Delhi for the award of a fellowship.
REFERENCES
1. B.C. Syrett, Corrosion, 32, 242, 1976.

2. A. Powell Carol, Int. Biodeterior. Biodegrad., 34, 321, 1994 (Publ.
1995).
3. A.H.L. Chamberlain and B.J. Garder, Biofouling, 1, 79, 1988.
4. F.L. LaQue, J. Am. Soc. Naval Engrs., 53, 29, 1941.
5. S.Ya. Pidgaichuk, V.l. Grigovic, O.F. Sidethik, V.F. Tzurkam,
Fiz.-khim,. Mekh. Mater, 29, 127, 1993.
6. H.A. Videla, M.F.L.de Meie and G.A. Brankevich, Corrosion 89,
Ν ACE, New Orleans, Louisiana, Paper No.291, 1989.
7. L.E. Eiselstein, B.C. Syrett, S.S. Wing and R.D. Caligiuri, Corros.
Sei., 23, 223, 1983.
8. C. Kato, J.E. Castle, B.G. Ateya and H.W. Pickering, J. Electrochem.
Soc., 127, 1897, 1980.
9. R. Francis, Brit. Corros. J., 20, 167, 1985.
10. F.J. Ijselling, J.M. Kroughman and L.J. Drolenga, Proceedings of the
5"' Intern. Congress of Marine Corrosion and Fouling, Barcelona,
Spain, 1980, p. 146.
11. Dr. Phil Max Hansen, 'Constitution of binary alloys', Second Edition,
McGraw-Hill Book Company, Inc., New York, 1958, P.601.
12. A.W. Tracy and R.L. Hungerford, Proc. ASTM, 45, 591, 1945
13. G.L. Bailey, J. Inst. Metals, 79, 243, 1951.
14. E.W. Palmer and F.H. Wilson, J. Metals, 4, 55, 1952.
15. P.T. Gilbert and F.Laque, J. Electrochem. Soc., 101, 448, 1954.
95
Authenticated
An Overview
16. W. Katz, Werkstoffe Korrosion, 15, 977, 1964.

17. W.C. Stewart and F.L. LaQue, Corrosion, 8, 259, 1952.
18. A.M. Beccaria and J. Crousier, Brit. Corros. J., 26, 215, 1991.
19. H.H. Uhlig, 'Corrosion Hand Book\ John Wiley & Sons, 1948.
20. N.B. Pilling and R.E. Bedworth, Ind. Eng. Chem., 17, 372, 1925.
21. R.L. Levin and J.B. Wagner, J. Electrochem. Soc., 108, 954, 1961.
22. S. Miyake, Sei. Papers, Inst. Phys. Chem. Research (Tokyo) 31, 161,
1937.
23. J.E. Castle and M. Nasserian-Riab, Corros. Sei., 15, 537, 1975.
24. J.E. Castle, Corros. Sei., 19, 475, 1979.
25. F.H. Stott and G.C. Wood, Corros. Sei., 19, 961, 1979.
26. D.D. Whittle and G.C. Wood, Corros. Sei., 8, 295, 1968.
27. K.D. Efird, Corrosion, 31, 77, 1975.
28. W. Clapp, Trans. Electrochem. Soc., 87, 103, 1945.
29. C. Bulow, Corrosion Hand Book, edited by H.H. Uhlig, John Wiley &
Sons, New York, 1948, P.85
30. Proc. Am. Soc. Testing Materials, 44, 224, 1944.
31. Data from International Nickel Co.
32. G.W. Kammlott, J.P. Franey and T.E. Graedel, J. Electrochem. Soc.,
131, 505, 1984.
33. G.W. Kammlott, J.P. Franey and T.E. Graedel, J. Electrochem. Soc.,
131,511, 1984.
34. B. Chattopadhyay and S. Sadigh-Esfandiary, Corros. Sei., 13, 747,
1973.
35. B.D. Bastow and G.C. Wood, Corros. Sei., 18, 275, 1978.
36. B.D. Bastow and G.C. Wood, Corros. Sei., 18, 297, 1978.
37. Η.P. Dhar, R.E. White, G. Burnell, L.R. Comwell, R.B. Griffin and R.
Darby, Corrosion, 41, 317, 1985.
38. M.H. Wadhan, A.Y. Abdel Latief, Bull. Fac. Sei., Assiat Univ., B, 24,
155, 1995.
39. R. Robler, J. Genesca, Afmidad, 48, 25, 1991.
40. H.P. Lee and Ken Nobe, J. Electrochem. Soc., 132, 1031, 1985; 133.
2035, 1986.
41. C. Kato, B.G. Ateya, J.E. Castle and H.W. Pickering, J. Electrochem.
Soc., 127, 1890, 1980.
42. W.H. Smyrl, in: Comprehensive Treatise of Electrochemistry, Vol.4,
J.O'M. Bockris, B.E. Conway, E. Yeager and R.E. White, Editors, p.
97, 1981.

Authenticated
43. H.P. Dhar, R.E. White, R. Darby, L.R. Cornwell, R.B. Griffin and G.
Burnell, Corrosion, 41, 193, 1985.
44. C. Kato and H.W. Pickering, J. Electrochem. Soc., 131, 1219, 1984.
45. R.F. North and M.J. Pryor, Corros. Sei., 10, 297, 1970.
46. R.G. Blundy and M.J. Pryor, J. Electrochem. Soc., 12, 65, 1972.
47. J.M. Popplewell, R.F. Hart and J.A. Ford, J. Electrochem. Soc., 13,
295, 1973.
48. D.P. Harvey, T.S. Sudarshan and M.R. Louthan, Jr., Brit. Corros. J.,
2 3 , 6 1 , 1988.
49. H. Hack and H. Pickering, Electrochemical Impedance Analysis &
Interpretation (Proc. Conf.), San Diego, California, United States,
1991 Nov.
50. H. Hack and H. Pickering, ASTM Spec. Publ., 1993, 220-36.
51. O. Kubaschewski and B. Hopkins, "Oxidation of metals and alloys",
p.21, Buttersworth, London, 1967.
52. H.P. Hack and H.W. Pickering, J. Electrochem. Soc., 138, 690, 1991.
53. F. Mansfeld and H.H. Uhlig, Corros. Sei., 9, 377, 1969.
54. H.H. Uhlig, Eleclrochimica Acta., 16, 1939, 1971.
55. Zhu Xiaolohg, Lin Leyun and Yan Yumin, Cailiao Kexue jinzhan, 6,
218, 1992.
56. M. Abdallah, A.Y. Eletre and A.I. Mead, J. Electrochem. Soc. India.,
4 5 , 7 1 , 1996.
57. P.K. Chauhan and H.S. Gadiyar, Corros. Sei., 25, 55, 1985.
58. J.O'M. Bockris, B.T. Rubin, A. Despic and B. Loverecek,
Electrochim. Acta., 17, 973, 1972.
59. B. Cahan and R. Haynes, J. Electroanal. Chem., 22, 339, 1969.
60. M.E. Walton and P.A. Brook, Corros. Sei., 17, 317, 1977.
61. M.E. Walton and P.A. Brook, Corros. Sei., 17, 593, 1977.
62. H.P. Lee and Ken Nobe, J. Electrochem. Soc., 131, 1236, 1984.
63. H.P. Lee and Ken Nobe, J. Electrochem. Soc., 140, 2483, 1993.
64. Ken Nobe and G.L. Bauerle, Corrosion, 37, 426, 1981.
65. F.K. Crundwell, Electrochim. Acta, 36, 2135, 1991.
66. R.D.K. Misra and G.T. Burstein, Corros. Sei., 24, 305, 1984.
67. P. Druska, H.H. Strehblow and S. Golledge, Corros. Sei., 38, 1369,
1996.
68. I. Milosev and M. Metikos-Hukovic, J. Electrochem. Soc., 138, 61,
1991.
69. I. Milosev and M. Metikos-Hukovic, Corrosion, 48, 185, 1992.

97
Authenticated
An Overview
70. I. Milosev and M. Metikos-Hukovic, Electrochim. Acta, 42, 1537,

1997.
71. M. Metikos-Hukovic and I. Milosev, J. Appl. Electrochem., 22, 448,
1992.
72. P. Druska and H.H. Strehblow, Corrosion Control Low-Cost Reliab.,
,h
Proc.-Int. Corros. Congr., 12 1993, 3951-72.
73. P. Druska, H.H. Strehblow and S. Golledge, Corros. Sei., 38, 835,
1996.
74. P. Druska and H.H. Strehblow, Surf. Interface. Anal., 23, 440, 1995.
75. F.L. LaQue and W.F. Clapp, Trans. Electrochem. Soc., 87, 103,1945.
76. J. Serre and J. Laureys, Corros. Sei., 5, 135, 1965.
77. B.C. Syrett, S.S. Wing and D.D. MacDonald, Annual Report to Office
of Naval Research, ONR Contract No. N00014-77-C-0046, NR
036-116 (February-1979).
78. F.L. LaQue and J.F. Mason, Amer. Pet. Inst. Division of Refining,
May, 1950.
79. A.W. Tracy and R.L. Hungerford, Proc. Amer. Soc. Test. Mat., 45,
591, 1945.
80. M. Tavi, D. Forsen, S.Y. Iasaari and J. Kukkonen, Scand. Corros.
th
Congr. Eurocorr '92, 12 1992, 1, 739-747.
81. B.J. Little and F.B. Mansfeld, Werkstoffe und Korrosion, 42, 331,
1991.
82. A.M. Beccaria and J. Crousier, Brit. Corros. J., 24, 49, 1989.
83. J. Crousier and A.M. Beccaria, Werkstoffe und Korrosion, 41, 185,
1990.
84. H.E. Stores, Corrosion, 17, 461t, 1961.
85. K.D. Efrid and D.B. Anderson, Materials Protection and
Performance, 14, Nov.37, 1975.
86. D.C. Vreeland, Materials Protection and Performance, 15, Oct.38,
1976.
87. D.D. Massden, Materials Protection and Performance, 17, Aug.9,
1978.
88. John M. Schlüter, Materials Protection and Performance, 17, Feb.25,
1978.
89. G. Gurmano, C. Simoncelli, N.M. Valota and E. Traversa,
Desalination, 74, 259, 1989.
90. F.P. Ijsseling, Proc. Understanding Prev. Corros., 10th Eurr. Corros.,
1993,2, 1040-6.

98 Authenticated
91. S.S. Sawant, D. Khandeparker, A. Tolarkar, K. Venkat and A. Karg,

Indian. J. Chem. Technol., 2, 322, 1995.
92. K.K. Satpathy, M.P. Srinivasan, S. Rangarajan, S.V. Narashiman and
P.K. Mathur, Bull. Electrochem., 12, 64, 1996.
93. Zhu Xiaolong, Lin Leyun and Lei Tingquan, Rare Met. (Beijing), 16,
16, 1997.
94. Zhu Ziaolong, Lin Leyun and Xu Jie, Lei Tingquan, Cailiao Kexue Yu
Congyi, 5,21, 1997.
95. R.B. Niederberger, J.P. Gudas and G.J. Danek, NACE Corrosion/76,
Houston, Texas, Paper No. 76, 1976.
96. Barry Syrett, Corros. Sei., 21, 187, 1981.
97. D.D. MacDonald, B.C. Syrett and S.S. Wing, Corrosion, 34, 289,
1978.
98. H.H. Lu and D.J. Duquesse, Corrosion, 46, 843, 1990.
99. F.P. Ijsseling, L.J.P. Drolenga and B.H. Kolster, Brit. Corros. J., 17,
162, 1982.
101. Ralph W. Ross and David B. Anderson, Materials Protection and
Performance, 14, Sept. 27, 1975.
102. Y.Z. Wang, A.M. Beccaria and C. Poggi, Corros. Sei., 36, 1277, 1994.
103. A.M. Beccaria, G. Poggi and Y.Z. Wang, Werkstoffe Korrosion, 45,
562, 1994.
104. A.M. Beccaria, Y.Z. Wang and G. Poggi, Surf. Interfac. Anal., 21,
442, 1994.
105. L. Admiral, F.P. Ijsseling, B.H. Kolster and J. Van Der Veer, Brit.
Corros. J., 21, 33, 1986.
106. R.S. Ben and H.S. Campbell, 1" Int. Congr. Metallic Corrosion,
London, England, 1961, p. 630.
107. W.E. Heaton, Brit. Corros. J., 13, 57, 1978.
108. P.T. Gilbert, Brit. Corros. J., 14, 20, 1979.
109. R.J.K. Wood, S.P. Hutton and D.J. Schiflrin, Corros. Sei., 30, 1177,
1990.
110. P.T. Gilbert, Materials Protection and Performance, 21, Feb., 1982.
111. T. Howard Rogers, Marine Corrosion, George Newner Ltd., Tower
House, Southampton St., London, 1968.
112. B.C. Syrett and S.S. Wing, Corrosion, 36, 73, 1980.
113. L. Giuliani and G. Bombara, Brit. Corros. J., 8, 20, 1973.

99
Authenticated
An Overview
114. F.L. LaQue, Marine Corrosion, Wiley-Interscience, New York, 1975,

P. 258.
117. C. Mansfredi, S. Simison and S.R. deSanchez, Corrosion, 43, 458,
1987.
118. P. Traverso, A.M. Beccaria and G. Poggi, Brit. Corros. J., 29, 110,
1987.
119. Jamal Ν. Al-Hajji and Mahmoud R. Reda, J. Electrochem. Soc., 142,
2944, 1995.
120. J.N. Al-Hajji and M.R. Reda, J. Electrochem. Soc., 141, 1432, 1994.
121. J.N. Al-Hajji and M.R. Reda, Corrosion, 49, 809, 1993.
122. M.R. Reda and J.N. Al-Hajji, Brit. Corros. J., 30, 56, 1995.
123. J.F. Bates and J.M. Popplewell, Corrosion, 31, 269, 1968.
124. John P. Gudas and Harvey P. Hack, Corrosion, 35, 259, 1979.
125. F.L. LaQue, Marine Corrosion Causes and Prevention, John Wiley
and Sons, New York, p. 122-123, 1975.
126. K. Kawai, Journal of the Japan Copper and Brass Research
Association, 11, 119, 1972.
127. J. A. Carew and M. Islam, Ν ACE International, 1994, Paper No. 491,
p. 14.
128. S. Sato, Japan Journal of Thermal Power, 31, 295, 1970.
129. D.R. Lenard, J.G. Moures and G.E. Morin, Brit. Corros. J., 24, 19,
1989.
130. J.N. Al-Hajji and M.R. Reda, Corros. Sei., 34, 163, 1993.
131. Reda R. Mahmoud and Jama! Ν. Al-Hajji, J. Univ. Kuwait Sei., 20,
171, 1993.
132. Reda R. Mahmoud and Jamal Ν. Al-Hajji, Corros. Control. Low-Cost
Reliab., Proc.-Int. Corros. Congr., 12'h, 1993, 3587-99.
133. A. El Domiaty and J.N. Al-Hajji, J. Mater. Eng. Perform., 6, 534,
1997.
134. Reda R. Mahmoud and Jamal Ν. Al-Hajji, ASTM Spec. Tech. Publ.,
1997, STP 1300 (Corr. Testing in natural water - II Vol.) 143-158.
135. F.A. Richards, in: Riely and Skirrow, Ed., Chemical Oceanography,
Academic Press, NewYork, Vol.1, p.611, 1965.
136. J.F. Bates and J.M. Popplewell, Corrosion, 31, 269, 1975.
137. J.P. Gudas and H.P. Hack, Corrosion, 35, 67, 1979.
138. D.D. MacDonald, B.C. Syrett and S.S. Wing, Corrosion, 35, 367,
1979.
100 Authenticated
139. D.D. MacDonald, B.C. Syrett and S.S. Wing, Ν A C E Corrosion/78,

Houston, Texas, Paper No.25, 1978.
140. D.D. MacDonald, B.C. Syrett and S.S. Wing, Annual Report to Office
of Naval Research, ONR Contrat No. N00014-77-C-0046, NR
036-116 (February-1978).
141. B.C. Syrett, Corrosion, 32, 257, 1977.
142. B.C. Syrett, D.D. MacDonald and S.S. Wing, Corrosion, 35, 409,
1979.
143. L.E. Eiselstein, B.C. Syrett, S.S. Wing and R.D. Caligiuri, Corros.
Sei., 23, 223, 1983.
144. Μ. Islam, W.T. Riad, S. Al-Kharraz and S. Abo-Namous, Corrosion,
47, 260, 1991.
145. M. Islam and S. Abo-Namous, Corrosion, 47, 654, 1991.
146. K. Habib and A. Husain, Desalination, 97, 29, 1994
147. A.M. Beccaria, G. Poggi, P. Traverso and M. Ghiazza, Corros. Sei.,
32, 1263, 1991.
148. Η.P.Hack and J.P.Gudas, Mater. Perform., 18, 25 (Mar. 1979)
149. L.E. Eiselstein, B.C. Syrett, S.S. Wing and R.D. Caligiuri, N A C E
Corrosion, Reprint 59(1982).
150. D.D. Macdonald, B.C. Syrett and S.S. Wing, Corrosion, 35, 367,
1979.
151. C. Kato, H.W. Pickering and J.E. Castle, J. Electrochem. Soc., 131,
1225, 1984.
152. T.L. Woods, Gov. Rep. Announce. Index (U.S), 1992, 92(19)
153. S. Sato, Japan Inst, of Metals Journal, 28, 48, 1964.
154. J.M. Popplewell, Corros. Sei., 13, 593, 1973.
155. Ζ. Ahmad and B.J. Abdul Allem, Desalination, 95, 307, 1994.
156. D.J. Schiffrin and S.R. De Sanche, Corrosion, 41, 31, 1985.
157. K.S. Rajagopalan, M. Raghavan, N.S. Rengaswamy, T.M.
Balasubramanian and V.S. Muralidharan, Materials Protection and
Performance, 20, 19, (Jan. 1981).
158. C. Prasad, Ramakrishna, R. Somasundaram, R. Vasudevan., Prakt.
Metallogr., 28, 15, 1991.
159. C.E. Zobel!, J. Bacteriol., 46, 39, 1943.
160. H.M. Horburd and A. Freiberger, Ocean Eng., 1, 637, 1970.
161. E.J.F. Wood, Aust. J. Marine Freshwater Res., 1, 85, 1950.
162. E.J.F. Wood, Microbiology of Oceans and Estuaries, Elsevier,
Amsterdam, 1967.
101
Authenticated
An Overview
163. M.F.L. de Meie, G. Brankevich and H.A. Videla, Brit. Corros. J., 24,
211, 1989.
164. M.F.L. de Meie, G. Brankevich and H.A. Videla, Corros. Reviews, 9,
269, 1990.
165. M.F.L. de Meie, G. Brankevich and H.A. Videla, Proc. 7lh Int. Congr.
Mar. Corr. and Fouling, Valencia, Spain, 1988.
166. M. F.L. deMeie, An.-CIDEPINT, 1992, 259-78.
167. S.G. Gomez de Saravia, M.F.L. de Meie and H.A. Videla, Biofouling,
7, 141, 1993.
168. M.B. McNeil, J.M. Jones and B.J.Little, Corrosion, 47, 674, 1991.
169. A.H.L. Chamberlin, S.E. Simmonds and B.J.Gasner, Int. Biodeterior,
2 4 , 2 1 3 , 1988.
170. H.A. Videla, S.G. Gomez de Saravia and M.F.L. de Meie, Corrosion
89, NACE, N e w Orleans, Louisiana, Paper No. 185, 1989.
171. H. Cypionka, F. Widdel and N. Fenning, FEMS Microbiol Ecol., 31,
39, 1985.
172. J.W. Costerton, G.G. Geesey and P.A. Jones, Mater. Performance, 27,
49, 1988.
173. H.A. Videla, M.F.L. deMeie and G. Brankevich, Corrosion, 44, 423,
1988.
174. S.G. G o m e z de Saravia, M.F.L. deMeie and H.A. Videla, Corrosion,
46, 302, 1990.
175. F. Mansfeld and B. Little, Electrochim. Acta, 37, 2291, 1992.
176. B. Little, P. Wegner, J. Jacobus and L. James, Estuaries, 12, 138,
1989.
177. P.A. Wagner, A.V. Stiffey and B.J. Little, Gas, Oil, Coal, Environ.
Biotechnol., 3, 3rd, 1990, Pub. 1991, 521-33.
178. R.O. Lewis, Mater. Perform., 21, 31, (Sept.1982).
179. R.B. Srinivasan, S.N. Gaonkar and A.A. Karande, Proc. Indian Acad.
Sei. (Anim. Sei.), 99, 163, 1990.
180. Β. Little, R. Ray, P. Wagner, F. Mansfeld, R. Tsai and H. Shih, Proc.
Electrochem. Soc., 91, 7, 1997.
181. J. Mathiyarasu, C. Stella, S. Maruthamuthu, N. Palaniswamy, A.
Rajendran and N.S. Rengaswamy, Proc. National Symposium on
Electrochemistry in Nuclear Technology, 1998, p. 196.
182. J. Mathiyarasu, S. Maruthamuthu, N. Palaniswamy and P. Ganapathy,
Proc. Eigth National Congress on Corrosion Control, 1998, p. 4.3.1.

Authenticated
183. J.S. Maki, B.J. Little, P. Wagner and R. Mitchell, Biofouling, 2, 27,
1990.
184. F. Mansfeld, G. Liu, H. Xiao, C.H. Tsai and B.J. Little, Corros. Sei.,
36, 2063, 1994.
185. Tseng Ming Don and Shih Ham Chang, Corros. Prev. Control, 41, 19,
1994.
186. R.F. North and M.J. Pryor, Corros. Sei., 8, 149, 1968.
187. J.Ε. Castle, D.C. Epler and D.B. Peplow, Corros. Sei., 16, 145, 1970.
188. D.C. Epler and J.E. Castle, Corrosion, 35, 451, 1979.
189. D.C. Lenard, J. Moures and G.E. Morin, Brit. Corros. J., 24, 19, 1989.
190. R. Francis, Mater. Perform., 21, 44, (Aug-1982).
191. P.R. Shibad, J. Electrochem. Soc. India, 44, F60, 1995.
192. T.W. Bostwick, Corrosion, 17, 12, 1961.
193. J.C.J. Rowlands, Applied Chemistry, 15, 57, 1965.
194. D. Chadwick and T. Hashemi, Corros. Sei., 18, 39, 1978.
195. P.H.S har, W Li and K. Nobe, Proe. Electrochem. Soc., 93, 2, 1993.
196. T.S. Lee, Corrosion, 39, 371, 1983.
197. B.D. Oakes, Material Protection and Performance, 15, 44 (Jan-1976).
198. D. Van Loyen, Werkst. Korros., 40, 559, 1989.
199. P. Vander Pool Daniel and Y.Cha Charles, Eur. Pat. Appl. Ep., 397,
454, 1989, p.13.
200. P.Vander Pool Daniel and Y.Cha Charles, Eur. Pat. Appl. Ep., 478,
247, 1990.
201. A. Omberger John, A. Kelly John and B. Batton Carol., Can. C.A., 1,
2 9 3 , 6 1 3 , 1991.
202. Hollander Orin, Eur. Pat. Appl. Ep., 479, 572, 1992.
203. P. Vander Pool Daniel and P. Reysusan, Eur. Pat. Appl. Ep., 481, 667,
1990.
204. Jamal Ν. Al-Hajji and Mahmoud R. Reda, Ind. Eng. Chem. Res., 32,
960, 1993.
205. M.A. Elmorsi, M.M. Ghoneins and E.M. Mabronk, J. Electrochem.
Soc. India, 41, 97, 1992.
206. R. Gasparini, C. Delia Rocca and E. loannilli, Corros. Sei., 10, 157,
1970.
207. Η.P.Hack and J.P.Gudas, Materials Performance, 19, 49, 1980.

103
Authenticated

Corrosion Resistance of Cupronickels - An Overview PDF

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Corrosion Resistance of Cupronickels - An Overview PDF

Uploaded by

Copyright:

Available Formats

CORROSION RESISTANCE OF

J. Mathiyarasu, N. Palaniswamy and V.S. Muralidharan

Corrosion Science and Engineering Division,

Brought to you by | Purdue University Libraries

Cupronickel alloys have been extensively used in marine and offshore

Brought to you by | Purdue University Libraries

Alloys of copper with nickel are called cupronickels with nickel

Brought to you by | Purdue University Libraries

1. The cupronickels which contain 20 to 30 % nickel, remainder copper,

Brought to you by | Purdue University Libraries

pit and crevice formation as a result of segregation of nickel-iron rich

Properties 80/20 alloy 70/30 alloy

The rate of oxidation of cupronickels (up to 3 0 % nickel) is not

Brought to you by | Purdue University Libraries

Fig. 1: Oxidation of copper-nickel alloys /20/.

Ni(in alloy) + C u 2 0 -> NiO + 2Cu

70 Brought to you by | Purdue University Libraries

Oxidation of copper-10 nickel and copper-24 nickel at 800°C produces

The potential-pH diagram of 90/10 and 70/30 cupronickels in natural

Brought to you by | Purdue University Libraries

Fig. 2: Pourbaix diagram of cupronickel alloys 1211.

The overall region where maximum pitting and biofouling occur is

72 Brought to you by | Purdue University Libraries

Fig. 3: Behaviour of cupronickel alloys in seawater/19/

Cupronickels are the most corrosion resistant of the commercial

Environment 70/30 80/20 90/10

sections, the corrosive properties of cupronickel alloys are reviewed

5.1 Atmospheric Corrosion

Test site Corrosion rate in ipy

sulphidisation. Thus copper-10% nickel alloy sulphidised faster than

5.2 Corrosion Behaviour in Aqueous Solutions

is unfilled, i.e. for copper content up to 40%, conditions favouring the

Brought to you by | Purdue University Libraries

5.2.2. In Acidic Solutions

78 Brought to you by | Purdue University Libraries

mV/dec. and 70 mV/dec. without and with chloride (3 χ 10"4M) addition.

5.2.3. In Alkaline Solutions

Brought to you by | Purdue University Libraries 79

layer overlying a Cu 2 0 barrier layer, which contained incorporated nickel

5.3 Corrosion in Marine Environment

5.3.1. Effect of oxygen content

80 Brought to you by | Purdue University Libraries

Cu + 2C1 — CuCl 2 " + e'

The solid C u 2 0 then forms by hydrolysis of the CuCl 2 " complex,

CUCI 2 " + H 2 0 C u 2 0 + 4C1" + 2 H +

This reaction is autocatalytic with respect to copper and also resulted in

Thus, the hydrolysis reaction is enhanced because of the availability of

Brought to you by | Purdue University Libraries 81

4CUC12" + H 2 0 + V2O2 -> 2Cu 2 0 + 8C1" + 2H+

5.3.2. Effect of temperature

82 Brought to you by | Purdue University Libraries

5.3.3. Effect of velocity

Brought to you by | Purdue University Libraries

surface encouraged 'shielded area attack' under the debris. Therefore, it is

5.3.4. Effect of pollutants

84 Brought to you by | Purdue University Libraries

Alloy Pipe sizes

and by improper dumping of municipal wastewater. These pollutants often

5.3.4.1. Sulphide pollution

Brought to you by | Purdue University Libraries85

86 Brought to you by | Purdue University Libraries

smooth and nonporous, while the pre-exposure to sulphide resulted in the