EFFECT OF SEAWATER LEVEL ON CORROSION

BEHAVIOR OF DIFFERENT ALLOYS1

Saleh A. Al-Fozan and Anees U. Malik
Saline Water Desalination Research Institute
Saline Water Conversion Corporation (SWCC)
P.O.Box 8328, Al-Jubail 31951, Saudi Arabia.
E-mail: rdc@swcc.gov.sa

ABSTRACT
Seawater is one of the most corroded and most abundant naturally occurring
electrolyte, covering about 70% of the earth's surface. The corrosivity of the seawater
is reflected by the fact that most of the common structural metals and alloys are
attacked by this liquid or its surrounding environments.

The laboratory immersion test technique has been used to evaluate the effect of
seawater level on corrosion behavior of different alloys. In three sets of experiments,
carbon steels (G1010 and 1020), 304 SS, 316L SS, 90/10 Cu/Ni, 70/30 Cu/Ni, Incoloy
825 and Inconel 625 were utilized.

The specimens were fixed at three locations namely: above seawater surface, semi
submerged in seawater and fully submerged in seawater. The experiments have been
carried out at room temperature with very slow seawater movement (12 lit/hrs). The
exposure time was varied between one to two years.

In this study the corrosion behavior of different alloys has been evaluated based on
exposure location. Beside corrosion rate calculations, the localized attack has also
been evaluated.
1.

INTRODUCTION

Seawater is one of the most corroded and most abundant naturally occurring electrolyte.
The corrosivity of the seawater is reflected by the fact that most of the common
structural metals and alloys are attacked by this liquid or its surrounding environments.

This paper has been presented at International Desalination Association (IDA) World Congress
Conference held at Singapore in 2005.

The seawater environments can be divided into five zones namely: subsoil,
continuously submerged, tidal, splash zone above high tidal and atmospheric zone [1].

The corrosion behavior of metals and alloys differ from one zone to another. In splash
zone the stainless steels have usually satisfactory performance while, the carbon and
low alloy steels do not. Anderson and Ross had found that the austenitic grades
performed much better than martensitic and ferritic grades [2]. The Ni, Cu and P
alloyed steels were found to be much more resistant than carbon steel in splash zone
[3]. Also, it was found that Mn, P and Al had measurable influence on corrosion rates
of low carbon steels under tidal exposure. After 5 years exposure test it was found that
the rate of attack in splash zone was much higher than the atmosphere and deep
submerged zones [4].

Oxygen, biological activities, pollution, temperature, salinity and velocity are the major
factors which affected the corrosion behavior of materials in the submerged zone. The
corrosion behavior of conventional stainless steels indicates that pitting and crevice
corrosion are the most usual mode of attack in this zone [5]. The results of several
studies indicate that the alloys susceptible to corrosion will perforate within first years
of exposure, whereas the resistant alloys will exhibit no pitting attack for the full
exposure time of 8 to 18 months [6]. The depth of pitting at ambient air saturated
seawater after 16 months exposure was found to be 2.4 mm on 316L SS, while after 18
months exposure to deaerated seawater at 105oC, the pit depth was only 0.12 mm [7].
The corrosion rate and pitting potential of stainless steels in seawater are the functions
of Cr and Ni content, also the presence of alloys elements such Co, Mo and N has
significant and beneficial influence on the pitting and crevice corrosion resistance of
stainless steels [8]. The decease in corrosion rate of low alloy steels over the longer
periods was more gradual than that which was observed over the first year of exposure
[9]. To prevent pitting and crevice corrosion in austenitic stainless steel, 8% of
molybdenum content is required whereas for ferritic stainless steels, the amount is
approximately 25% chromium with 3.3% molybdenum [10].

In this paper the effect of different seawater levels on the corrosion behavior of some
structural alloys has been studied. Also, the influence of exposure time on corrosion
rate is evaluated.

2.

EXPERIMENTAL METHOD AND MATERIALS

Rectangular test specimens of different alloys with 50 20 2 mm in dimension were

utilized in the experimental work. Carbon steel (G1010 and 1020), Austenitic stainless
steel (AISI 304, and 316l SS), copper based alloys (90/10 Cu/Ni and 70/30 Cu/Ni) and
nickel based alloys (Incoloy 825 and Inconel 625) were used during the experiments.
The chemical compositions of the alloys are given in Table (1).

The specimens were exposed to seawater under different levels (above seawater level,
semi-submerged and immersed fully in seawater). Figure 1 shows the schematic
diagram of the experimental set-up. The seawater flow was kept very low (12/lit/hrs) at
room temperature. Weight loss coupon method technique had been used to determine
the corrosion rates. The test specimens were abraded on 400 grit SiC paper.

3.

RESULT AND DISCUSSION

Tables (2) through (9) show the corrosion rates of the alloys used at different exposure
sites and under different exposure time. The results show that the carbon steel G1020
has the maximum corrosion rate in all three locations whilst the inconel alloy 625
shows the lowest corrosion rate. Under fully immersed condition, there is a decrease in
corrosion rates with increasing of exposure time for all the test alloys. The reason for
this phenomenon may differ from alloy to alloy mainly depending on chemical
composition of the exposed alloy. For carbon steel, the corrosion product will be built
up on the surface which would reduce the mass transfer of oxygen and other agents to
the metal surface resulting in the reduction of the kinetic of the cathodic reactions.
Therefore, the increase in the corrosion product thickness will decrease the corrosion
rate. The corrosion product on the copper nickel alloys surface has the ability to protect
these alloys. This corrosion film is usually quickly formed on the alloy surface but it
takes considerably long time to reach a steady state. This corrosion film is usually
enriched by iron oxide and nickel oxide and therefore, the corrosion rate of copper
based alloys may be effected by iron content in the alloy composition and/or ferrous
ions in water stream. The decease in corrosion rate of stainless steel with time could be
attributed to the thickening of passive film on the alloy surface.

The corrosion rate of alloys at the above seawater level showed two different behaviors
compared with submerged location of the same alloy. In some cases the corrosion rate
at the above water level was higher than at the submerged location of the same alloy
whereas other alloys show different behavior. For 316L SS the corrosion rate at the
above water level was higher than the submerged location. The higher corrosion rate
above seawater is due to higher O2 concentration. A higher O2 concentration favors
cathodic reaction which tends to increase the rate of pit propagation after initial pitting.
For other alloys the corrosion rate at the above water level was lower than the
submerged location of the same alloy. The increasing of pitting density and pit depth on
304 SS in submerged location compared with above water level location resulted in
increased corrosion rate of this alloy at submerged location. This phenomenon was also
observed on alloy 825 but to a lesser extent. The increase of corrosion rate of alloy 625
in submerged location compared with above water level location could be attributed to
the thickening of passive film in submerged location. The alloy 625 was found free
from the pitting in all of the two locations.

The corrosion rates of the specimens at semi-submerged location for all the tests are
higher than the other locations. The most effected area in test specimens was found at
water line zone. This attack could be due to the formation of differential aeration cell.
Due to low oxygen solubility in water the oxygen concentration will be higher above
the water surface. The pitting with different depths was found in all the alloys surface
except alloy 625. The maximum depth of attack was found to follow the sequence (in
decreasing order):

Carbon steel > 304 S> 316L SS > 90/10 Cu/Ni> 70/30 Cu/Ni> alloy 825.

Table (10) shows the pit depth corrosion results on stainless steel alloys. Figure (2)
through Figure (4) shows the relation between molybdenum content and corrosion rate
in three locations namely, above seawater level, semi-submerged and submerged,
respectively. In all the three figures the corrosion rate decreases with increasing
molybdenum content. In semi-submerged and submerged conditions, the rate of
decreasing corrosion rate of Incoloy 825 as compared with 316L SS could be attributed
to the high content of chromium in Incoloy 825.

Figure (5) through Figure (7) show the relation between molybdenum content and pit
depth for different alloys exposed at above seawater level, semi-submerged and
submerged respectively. In semi-submerged area the high level of chromium content
and presence of titanium to Incoloy 825 are responsible for decreasing of pit depth as
compare with 316L SS which has similar level of molybdenum content.

The Pitting Resistance Equivalent with nitrogen consideration (PREN) was calculated
for stainless steel and nickel based alloys following the equation:
PREN = % Cr + 3.3 % Mo + 16 % N
The relations between PREN and pit depth at three locations (above seawater level,
semi-submerged and fully merged) are shown in Figure (8) through Figure (10)
respectively. In submerged zone at low values of PREN, small change in PREN will
give significant change in pitting resistance at propagation stage. But at high value of
PREN, the change in pit depth is small with changing of PREN. At semi-submerged and
above seawater level locations, significant improvement in pitting resistance is found at
propagation stage with increasing PREN.

4.

CONCLUSIONS

1.

The corrosion rate of carbon steel (G1020) are the highest at all the three
locations, namely, above the seawater, partial submerged and fully
submerged. While the Inconel alloy 625 has the lowest corrosion rate at all
three locations.

2.

The most severe corrosion for alloys used are observed at partially
submerged zone as compared to other locations.

3.

The carbon steel, 304 SS and 316L SS have been markedly affected by
water line corrosion.

4.

With increase of nickel content in copper base alloys the resistance to water
line corrosion increases.

5.

Titanium addition to Incoloy 825 has beneficial effect at semi-submerged

location in minimizing the pitting depth.

5.

REFERENCES
1.
2.

3.
4.
5.
6.

7.
8.
9.
10.

Element
Material
G1010
G1020
304 SS
316L SS
90/10
Cu/Ni
70/30
Cu/Ni
Incoloy
825
Inconel
625

F. L. LaQue, "Marine corrosion and prevention", p. 116, John Wiley &sons,

1975.
D. B. Anderson and R. W. Ross Jr., "Proection of steel piling in marine
splash and spray zone-Metallic sheathing concept", Proceeding 4th
international congress on marine corrosion and fouling, France, pp. 461-473,
1976.
C. P. Larrablee, "Corrosion Resistant experimental steels for marine
application", 14 (11), 501-504, 1958.
A. A. Humbles, "The cathodic protection of steel in seawater", Corrosion,
September, 1949.
W. K. Boyd and F. W. Fink, "Corrosion of metals in marine environments",
Metal & ceramic information center report, MCIC-78-37, March, 1978.
F. M. Reinhart and J. F. Jenkins, "Corrosion of materials in surface seawater
after 12 and 18 months of exposure", Final report, NCEL-TN-1213
AD743872, January, 1972.
J. W. Oldfield and B. Todd, "Corrosion consideration in selected metals for
flash chamber", Desalination, no. 32, (1-3), 365, 1979.
A. U. Malik, N. A. Siddiqi, S. Ahmed and I. N. Andijani, Corrosion science,
37 (10), 1521-1535, 1995.
C. P. larrabee, "Corrosion resistance of high strength low alloy steel as
influenced by composition and environment", Corrosion, 9, 259-371, 1953.
H. P. Hack, "Corrosion behavior of 45 Mo-containing stainless steels in
seawater", Corrosion 82, paper no. 65, March, 1982.

Fe
Cr
Ni Mo Cu Mn
Bal 0.72 0.06 0.45 0.07 0.52
Bal
--------- 0.92
Bal 18.28 8.13 0.17 0.19 1.48
Bal 16.92 11.31 2.05 --- 1.04
1.41
--- 9.93 --- 88.18 0.273

Composition
C
S
N
0.1 0.016 --0.22 0.014 --0.047 0.01 0.076
0.021 0.004 0.048
0.001 0.002 ---

Si
0.13
0.24
0.49
0.46
---

0.53

0.02

0.01 0.003

---

30

--- 68.81 0.51

30.41 23.34 40.22 2.74 1.76

0.41

1.58 21.75 63.8 8.86

0.03 0.025 0.0005

---

0.02

---

---

0.001 ------ 0.17

P
Others
0.01
(Al-0.004)
0.019
--0.019
(Co-0.14)
0.028
--0.002 (Pb-0.004) & (Zn-0.155)

---

(Pb-0.01) & (Zn-0.08)

(Al-0.4) & (Ti-0.86)

0.04 0.005 (Ti-0.19) & (Al-0.13) &

(Nb-3.43) & (Co-0.01)

Table 1. Alloys chemical composition

Corrosion Rate (mpy)

Duration (days)
Type of exposure
Above seawater level

247
0.4287

500
0.4228

750
0.8164

Semi-submerged

2.3508

2.5154

2.8541

Fully submerged

1.5649

1.4983

1.2683

Table 2. Corrosion rate of carbon steel (G1010) in different exposure positions.

Corrosion Rate (mpy)

Duration (days)
Type of exposure
Above seawater level

247
0.6084

500
0.5823

750
0.6359

Semi-submerged

2.9278

3.1259

3.0717

Fully submerged

2.4364

2.416

2.1693

Table 3. Corrosion rate of carbon steel (G1020) in different exposure positions

Corrosion Rate (mpy)

Duration (days)
Type of exposure
Above seawater level

199
0.02731

402
0.0136

740
0.0117

Semi-submerged

0.02878

0.03145

0.0301

Fully submerged

0.01442

0.0219

0.0187

Table 4. Corrosion rate of AISI 304SS in different exposure positions

Corrosion Rate (mpy)

Duration (days)
Type of exposure
Above seawater level

199
0.00699

402
0.00344

740
0.0258

Semi-submerged

0.01409

0.02497

0.01893

Fully submerged

0.00961

0.00255

0.001963

Table 5. Corrosion rate of AISI 316L SS in different exposure positions

Duration (days)
Type of exposure
Above seawater level
Semi-submerged
Fully submerged

Corrosion Rate (mpy)

198
0.01233
0.11326
0.145

401
0.00548
0.1009
0.0821

Table 6. Corrosion rate of 90/10 Cu/Ni in different exposure positions

Duration (days)
Type of exposure
Above seawater level
Semi-submerged
Fully submerged

Corrosion Rate (mpy)

192
0.01463
0.08167
0.06734

365
0.00289
0.0977
0.04848

Table 7. Corrosion rate of 70/30 Cu/Ni in different exposure positions

Duration (days)
Type of exposure
Above seawater level
Semi-submerged
Fully submerged

Corrosion Rate (mpy)

252
0.003235
0.00405
0.00398

450
0.002195
0.005387
0.00266

Table 8. Corrosion rate of Incoloy (Alloy 825) in different exposure positions

Duration (days)
Type of exposure
Above seawater level
Semi-submerged
Fully submerged

Corrosion Rate (mpy)

252
0.00247
0.00312
0.0027

450
0.001193
0.00301
0.00188

Table 9. Corrosion rate of Inconel (Alloy 625) in different exposure positions

Exposure

Time
(days)

Type of
Exposure
Above sea water level
Semi-Submerged
Submerged

304 SS

316L SS
Incoloy 825
Pit depth (mm)

Inconel 625

199

402

740

199

402

740

252

450

252

450

0.31
0.73
0.52

0.47
1.08
1.38

0.93 0.18
1.38 0.58
1.54 0.21

0.36
0.81
0.39

0.65
.15
0.81

0.05
0.17
0.08

0.27
0.36
0.29

0
0
0

0
0
0

Table 10. Pitting depth results of stainless steels at different locations and exposure time

Seawater inlet

Specimens

Seawater Level

Specimen holder

Figure 1. Test container and specimen holder

Seawater outlet

0.014
0.012
0.01
0.008
0.006
0.004
0.002

Corrosion Rate (mpy)

0.016

0
10

Mo Content

Figure 2. Effect of Molybdenum Content on Corrosion Rate of Stainless

Steel for Specimens Located above Seawater Level

0 .03
0 .02 5
0 .02
0 .01 5
0 .01
0 .00 5

Corrosion Rate (mpy)

0 .03 5

0
10

M o Conte nt

Figure 3. Effect of Molybdenum Content on Corrosion Rate of Stainless

Steel for Specimens Located in Semi-Submerged Area

0.02
0.015
0.01
0.005
0
10

M o Content

Figure 4. Effect of Molybdenum Content on Corrosion Rate of Stainless

Steel for Specimens Located in Submerged Area

Corrosion Rate (mpy

0.025

10

Pit Depth (mm)

0.5
0.4 5
0.4
0.3 5
0.3
0.2 5
0.2
0.1 5
0.1
0.0 5
0
0

M o C o nte n t

Figure 5. Effect of Molybdenum Content on Pitting Depth of Stainless Steel

for Specimens Located above Seawater Level

1.2

0.8
0.6
0.4

Pit Depth (mm

0.2
0
10

Mo Content

Figure 6. Effect of Molybdenum Content on Pitting Depth of Stainless Steel

for Specimens Located in Semi-Submerged Area.

1.2

0.8
0.6
0.4

Pit Depth (mm)

0.2
0
10

Mo Content

Figure 7. Effect of Molybdenum Content on Pitting Depth of Stainless Steel

for Specimens Located in Submerged Area

0.5
0.4 5
0.4
0.3 5
0.3
0.2 5
0.2
0.1 5
0.1
0.0 5
0
60

50

40

30

20

10

PR E n

Figure 8. Effect of PREN Content on Pitting Depth of Stainless Steel for

Specimens Located above Seawater Level

1
0.8
0.6
0.4
0.2

Pittiing Depth (mm)

1.2

0
60

50

40

30

20

10

PREn

Figure 9. Effect of PREN Content on Pitting Depth of Stainless Steel for

Specimens Located in Semi-Submerged Area

1
0.8
0.6
0.4
0.2

Pitting Depth (mm

1.2

0
60

50

40

30

20

10

PREn

Figure 10.

Effect of PREN Content on Pitting Depth of Stainless Steel

for Specimens Located in Submerged Area