Paper No.

07249
THE USE OF CORROSION RESISTANT ALLOYS (CRAs) IN
COMPACT PLATE HEAT EXCHANGERS IN SEAWATER

Ola Persson
Alfa Laval
P.O. Box 74
SE-221 00 Lund, SWEDEN
ola.persson@alfalaval.com

Ladislav Novak
Consultant
Korskersv. 75
SE-226 50 Lund, SWEDEN

Karin Nilsson
Alfa Laval
P.O. Box 74
SE-221 00 Lund, SWEDEN

Daniel Klint
Alfa Laval
P.O. Box 74
SE-221 00 Lund, SWEDEN

ABSTRACT
Compact plate heat exchangers (CHE) are designed to optimize heat transfer. The corrugated plates
provide an immense surface through which heat can be transferred from one liquid or gas to another.
The basic plate heat exchanger consists of a series of thin, corrugated plates that are sealed with rubber
gaskets. The heat is transferred through the plate between the channels and complete counter-current
flow is created for highest possible efficiency.
Seawater is a complex solution of many salts containing living organisms, suspended silts, dissolved
gases and decaying organic materials. The metallic material generally used for CHE in seawater cooling
duties is titanium grade 1. The titanium material can stay passive due to a stable, protective and strongly
adherent oxide layer. Due to limited availability of titanium the delivery times of titanium has increased.
Consequently, it is vital to clarify the uniqueness of titanium and investigate alternative materials for use
in plate heat exchanger seawater applications.
A compact plate heat exchanger is, from a corrosion point of view, one of the most demanding
constructions for alloys whose corrosion resistance depends on a passive film. Crevices are formed both
in the contact points between the plates and under the rubber sealing gaskets. It is therefore relevant to
test under real conditions. In this paper, the use of corrosion resistant alloys (CRA) in plate heat
exchanger seawater applications are discussed and compared with the use of titanium.
Keywords: Compact plate heat exchangers, Heat transfer, Corrosion, Seawater, Titanium, Secool
Copyright
2007 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE
International, Copyright Division, 1440 South creek Drive, Houston, Texas 777084. The material presented and the views expressed in this paper are
solely those of the author(s) and are not necessarily endorsed by the Association. Printed in the U.S.A.

INTRODUCTION
Compact plate heat exchangers (CHE) are designed to optimize heat transfer and the corrugated
plates provide a large surface through which heat can be transferred from one liquid or gas to another.
Compared to shell-and-tube heat exchangers the CHE constructions have many advantages, e.g. the high
thermal efficiency and the small footprint. The basic plate heat exchanger consists of a series of thin,
corrugated plates with rubber gaskets between the plates. The heat is transferred through the plate
between the channels and a complete counter-current flow is created for highest possible efficiency. The
compact construction and the thin plates reduce the installation cost and provide a cost-efficient solution
to the customer. A schematic sketch of compact plate heat exchanger is shown in Figure 1.
Today a whole range of different compact plate heat exchanger products can be offered. The four
main groups are gasketed, brazed, fusion bonded or all-welded plate heat exchangers. Also tailor-made
plate heat exchangers made for special applications exist today, e.g. units that are designed for
evaporation and condensation duties. Depending on process conditions like physical properties of the
media and corrosiveness and pressure variations etc. different products fit to different situations.
In many processes, seawater is used as cooling medium on one side of the heat exchanger. One
example is the so-called secondary cooling applications (secool applications) where seawater often is
used to cool a loop with process water. In these secool applications there is a need of cooling huge heat
loads and therefore the heat exchangers must be very large to be able to handle the large flows. The
biggest CHE unit (T50) especially designed for secool applications working with seawater has a height
of nearly 4 m and can provide a maximum heat transfer surface of about 2900 m2 (31000 ft2).
SEAWATER CHARACTERISTICS AND PREVENTION OF BIOFOULING
Seawater is a complex solution of many salts containing living organisms, suspended silts, dissolved
gases and organic materials. Seawater aggressively corrode many materials mainly as a consequence of
the high chloride concentration, around 20 000 mg/l. Even if two water types appear to have a similar
composition, the corrosivity of the water can be very different1.
Natural seawater contains living organisms, which very fast can adhere to and form a biofilm on heat
exchanger surfaces. It is important to remove the biological fouling for many different reasons. For
instance, biofouling gives rise to a decreased thermal efficiency of heat exchanger surfaces and
increased friction losses in pipelines2. The biological film increases the corrosion potential of the
exposed metals and thus, also the risk of localized corrosion increases. Furthermore, when bacteria
harmful to metals are uncontrolled, microbiological influenced corrosion (MIC) of metals may occur3.
MIC of metallic materials does not involve any new form of corrosion. There is however no clear
reports showing that MIC have occurred in natural environments for highly alloyed stainless steels4.
The formation of biofouling can be prevented by different methods. The addition of biocides is the
most common method used in many industrial applications. Biocides can be divided into two categories;
a) oxidizing agents and b) non-oxidizing agents. Examples of oxidizing agents are chlorine,
hypochlorite, ozone, and chlorine dioxide. Some examples of non-oxidizing agents are bisthiocyanate,
formaldehyde, and quaternary ammonium salts4.
The most frequently used oxidizing biocide is chlorine or hypochlorite. Below pH 7.5 the hypochlorous acid, HOCl, predominates and above pH 7.5 hypochlorite ions, OCl-, predominates3. The
2

chlorination can be made continuously or intermittently (or combined). The mixture of hypochlorous
acid and hypochlorite ions is referred to as free available chlorine (FAC) or chlorine induced oxidants.
Chlorine or chlorine induced oxidants reacts quickly with oxidisable organic material present in the
seawater forming organic compounds. Chlorine also reacts with iron and manganese or other metallic
ions present. Consequently, the concentration of FAC is continuously reduced due to the reactions and
therefore the concentration is always highest in the dosing point.
Since chlorine and hypochlorite are strong oxidants, they alter the redox potentials of the water to
more noble values compared to natural, air-saturated seawater. Furthermore, the free corrosion
potentials of alloys in the passive as well as in the active state are increased. Of course, more noble
potentials increase the risk of localized corrosion. Stainless steels and nickel-base alloys are to varying
degrees much more sensitive to chlorination than titanium. In different test it has been reported that a
FAC level of about 0.1-0.2 ppm is sufficient to reduce the microbiological growth on steel surfaces close
to zero. The same effect has been observed with intermittent chlorination, if 1 ppm is dosed during 30
minutes per day5.
CORROSION RESISTANCE FOR DIFFERENT GROUPS OF CRAs IN
NON-CHLORINATED AND CHLORINATED SEAWATER APPLICATIONS
A compact plate heat exchanger is, from a corrosion point of view, one of the most demanding
constructions for alloys whose corrosion resistance depends on a passive film6. Crevices are formed both
in the contact points between the plates and under the rubber sealing gaskets. A wide range of materials
make it possible to use the compact plate heat exchanger in a very broad range of process applications.
Since the plate heat exchangers often are used with seawater on one side and a process medium on the
other side, it is essential not only to investigate the corrosion resistance to seawater, but also the
resistance to common process media like different kinds of acids. On the seawater side, the localized
corrosion attacks at the plate contact points and in the gasket grooves will be the limiting parameters.
Contradictory, on the process medium side it is likely that the general corrosion rate is the limiting
design parameter. A great knowledge of the corrosion resistance in different media is of outermost
importance when selecting materials in a compact plate heat exchanger.
Titanium grade 1 is the preferred material choice to use in compact plate heat exchangers running
with seawater. The market situation for titanium supply has, however, changed tremendously. Increased
usage with subsequent limitations in availability has caused increased delivery times of titanium.
Also in the past there have been troubles with long delivery of titanium, e.g. in the middle of the
1970s when a lot of titanium was used for submarine constructing. In this report, process experience of
seawater duties from the compact plate heat exchanger business is reported, including known limits for
alternative materials to titanium. Furthermore, results from the recent seawater corrosion tests at
SINTEF are presented.
Corrosion test at SINTEF
In the beginning of 2005, Alfa Laval started to test material alternatives in co-operation with the
Foundation for Scientific and Industrial Research at the Norwegian Institute of Technology (SINTEF) in
Norway to learn more about the limitations for seawater alternatives to titanium, e.g. super-austenitic
steels and nickel-base alloys.
3

The alternative plate heat exchanger materials were installed in real plate heat exchangers which were
exposed to seawater with a salinity of 3.3-3.6 % taken from the Cold North Sea (Trondheimsfjorden) at
a depth of 60 m. The water was processed into the test loop and the water was continuously exchanged
by fresh seawater with a rate of about 0.15-0.3 litre/minute. In the loop, the seawater was heated up by
an external heater to the correct temperature and both sides of the tested plate heat exchangers were
utilized for seawater exposure. Tests have been made both with and without chlorination (up to 1 ppm
continuously) at different temperatures up to 60C (140F). The total test time was 3 months. In the test
units the different plate materials were separated by plastic plates to avoid galvanic effects. Also the
carrying bars in the units were isolated. The test rig is illustrated in Figure 2 and a test unit is shown in
Figure 3. Table 1 and 2 show materials included in the test.
Titanium
Titanium was commercially introduced in the early 1950s since its high strength/density ratio made
the material especially interesting for the aerospace industry7. However, the excellent corrosion
resistance over a wide range of corrosion applications has resulted in the use of titanium also in many
non-aerospace applications. Some of the first installations using titanium in the chemical process
industry (CPI) were wet chlorine gas coolers8. For marine environments, titanium has been used in the
CPI for more than 40 years. As construction material for CHE titanium has been the primary choice in
seawater duties since the 1960s. Earlier, different types of copper-nickel alloys were often used, but one
main restrictive design parameter for this group of alloys was the low resistance to erosion-corrosion in
seawater service. When titanium was introduced it became possible to increase the velocities in the
channels and thus increase the thermal efficiency for CHE.
The mechanical properties of titanium are affected by small amounts of oxygen and nitrogen in solid
solution, and therefore a number of different grades of commercially pure titanium are available on the
market10. For plate heat exchanger manufacturing titanium grade 1 is the most commonly used due to
the good formability. The difference between grade 1 and 2 is that grade 1 is purer with regard to
impurities such as oxygen, iron, nitrogen, hydrogen and carbon. The increase of impurities increases the
strength (yield and tensile strength) of titanium but at the same time lowers the formability (elongation).
The superior corrosion resistance of titanium originates from the formation of a thin (typically 50-300
thick) stable, continuous, protective and strongly adherent oxide layer9. The oxide film is formed
spontaneously when fresh metal surfaces are exposed to air and/or moisture. In case the layer is
scratched it will almost instantly reformed because of the strong affinity to oxygen.
Unlike most other metals, the presence of chlorides does not detrimentally affect the protective layer
except under highly acidic reducing conditions and/or in combination with very high temperatures and
concentrations9. Titanium will stay passive up to at least 120C (250F) in CHE seawater applications,
according to field process experience, even if the seawater is chlorinated. The excellent resistance of
titanium to seawater is relatively unaffected by velocity and the material is not affected by typical
seawater contaminants like oxides, sulfides, sulfates10. Field experience and recent tests have shown that
no other metallic material in the same price level can replace titanium as CHE material in seawater
applications from a technical point, without restricting maximum operating temperatures, chlorination
levels, velocities, still-stands etc.

Nickel-base alloys
Nickel-base alloys have useful resistance to a wide variety of corrosive environments11. Different
nickel alloy families are available on the market, both binary and ternary alloys systems. One example
of a binary alloy system is the nickel-copper (Ni-Cu) alloys and one example of a ternary alloys system
is the nickel-chromium-molybdenum (Ni-Cr-Mo) alloys12.
The Ni-Cr-Mo nickel-base alloy group is the most commonly used nickel-base group for CHE. This
group is typically used in process applications like e.g. phosphoric acid and sulfuric acid production
plants. One material within this group frequently used for CHE process duties is the nickel-base alloy
N10276 (Alloy C-276). Other examples of Ni-Cr-Mo alloys are N06022 (Alloy C-22), N06200 (Alloy
C-2000), N06059 (Alloy 59) and N06686 (Alloy 686).
Due to the long delivery times of titanium, there is an on-going discussion regarding the possibilities
to use the nickel-base alloys as replacement alternatives to titanium in seawater CHE duties. Since
N10276 has been frequently used as CHE material in chemical process industries for about 30 years,
Alfa Laval has a lot of experience about its corrosion resistance and its limitations in different chemical
environments. For instance, N10276 is the primary alternative for high-concentrated sulfuric acid
coolers which are typically cooling down the sulfuric acid from about 80C (176F) by means of
seawater. Several references exist and one is Port Kembla Copper in Australia that was running for more
that 10 years without any problems on the seawater side. It is, however, very important to be aware of
that N10276 has a low corrosion resistance to oxidizing medias and cannot resist significant chlorination
levels, due to the relatively low chromium content13. Anyhow, it has previously been mentioned in this
report that a FAC level of about 0.1-0.2 ppm is sufficient to reduce the microbiological activity5.
Other examples of Ni-Cr-Mo materials used within Alfa Laval today are N06022 and N06200.
N06059 and N06686 are additional alternatives with quite similar chemical composition. Chemical
compositions of tested materials are given in Table 1. The seawater tests made in co-operation with
SINTEF showed that the Ni-Cr-Mo materials in this group are susceptible to corrosion in chlorinated
seawater at a temperature of 50C (122F) and at a FAC concentration of 1 ppm. After three months of
testing initial crevice corrosion attacks were found in the plate contact points. No differences between
the different alloys in this group were observed, all materials behaved in a similar way. A cross-section
of a plate contact point for the N06022 sample is shown in Figure 4. After measuring the corrosion
attacks it was possible to estimate the localized corrosion rate to 0.16 mm/y. The estimated lifetime of a
heat exchanger plate in this environment will therefore be about 3-4 years. Figure 5 shows N06200 and a
crevice corrosion attack in the plate contact point.
Admittedly, high chromium Ni-Cr-Mo materials cannot be considered as long-term seawater
alternatives to titanium without restricting the chlorination levels and seawater temperatures.
Stainless steel alloys
Stainless steels can be classified into three different main groups; austenitic steels, ferritic steels, and
duplex steels. Duplex steels in the annealed condition consist approximately of equal portions of
austenite and ferrite. Only the austenitic steels are today used as CHE material with respect to the
mechanical properties. The austenitic structure is characterized by a high tensile strength, good ductility
and formability. The reason for the good corrosion resistance of stainless steels is that they form a very
thin invisible surface film, i.e. the passive film. This film protects the steel from attack in corrosive
5

environments14. The most important alloying element is chromium, but a number of other elements such
as molybdenum, nickel and nitrogen also contribute to the corrosion resistance of stainless steels.
The resistance of stainless steels to pitting and crevice corrosion is often illustrated by the widespread
use of the Pitting Resistance Equivalent (PRE)1. Many examples of PRE expressions have been
published, but one of the most common is:
PRE = %Cr + 3.3%Mo + 16%N

(1)

A high PRE number relates to a high resistance to localized corrosion. The number is based on
experiments but a wide range of correlations exist, and the number should only be used as a rough
estimate of the localized corrosion properties of a metal.
At least 6 % Mo (super austenitic steels) is required in the stainless steel material to possess a
corrosion resistance sufficient for seawater applications. S31254 (254 SMO) is a super austenitic
material that has been used by Alfa Laval for about 25 years in different kinds of CHE applications.
According to field experience, S31254 can resist seawater in a plate heat exchanger at wall temperatures
below 35 C (95F) if the chlorination is restricted. Figure 6 shows the appearance of a heat exchanger
plate made of S31254 after three months testing in non-chlorinated seawater at a temperature of 60C
(140F). It is expected that all 6Mo stainless steels behave in a similar way. Therefore, the 6Mo stainless
steels cannot be considered as an alternative to titanium, at temperatures normally occurring in secool
CHE applications.
Some examples of super austenitic steels having higher contents of the important alloying elements
chromium, nickel, molybdenum, and nitrogen are today available on the market, the so-called 7Mo
stainless steels. Two examples from this group of alloys are S31277 (27-7Mo) and N08031 (Alloy 31).
Chemical compositions for these alloys and PRE values according to formula (1) are given in Table 2.
This group of alloys may be considered as alternatives to titanium in non-chlorinated seawater
applications, at least as temporary alternatives, but exposure tests in chlorinated seawater at 50C
(122F) and 1 ppm FAC gave rise to localized corrosion attacks both on S31277 and N08031. In Figure
7 the N08031 after testing is shown.
CONCLUSIONS
Field experience and recent tests have shown that no other metallic material in the same price level
can replace titanium as CHE material in seawater applications from a technical point, without restricting
maximum operating temperatures, chlorination levels, velocities, still-stands etc. It is therefore of
outermost importance to consider the long delivery times of titanium that today are present when new
projects are planned.
For non-chlorinated seawater applications the Ni-Cr-Mo alloys can be used as alternatives and field
experiences have showed that N10276 is possible to use in CHE seawater applications up to about 80C
(176F). For chlorinated seawater applications it is very important to be careful and follow instructions
given by the CHE supplier for each specific project.

REFERENCES
1.

Corrosion Handbook, Outokumpu Stainless, 2004.

2.

Walln B., Henrikson S.: Effect of chlorination on stainless steels in seawater, Werkstoffe und e
Korrosion 40, 602-615, 1989.

3.

Tuthill Arthur H., Avery Richard E., Lamb Stephen, Kobrin Gregory: Effect of chlorine on
common materials in fresh water, Paper No. 708, Corrosion 98.

4.

Philippe Marcus: Corrosion Mechanisms in Theory and Practice, Second Edition, Marcel
Dekker, In., 2002.

5.

Bengt Walln: Some factors Affecting Stainless Steel Corrosion in Seawater, Acom, no 4, 1990.

6.

Walln Bengt, Wegrelius Lena: Performance of a highly alloyed stainless steel in seawater
cooled plate heat exchanger, Eurocorr 2000.

7.

Corrosion (3rd Edition) Volumes 1-2, Edited by Shreir, L.L., Jarman R.A., Burstein G.T., Elsevier
1994.

8.

Uhligs Corrosion Handbook (2nd Edition), Edited by: Revie, R. Winston, 2000.

9.

R. W. Schutz: Titanium the technically correct metal for offshore seawater service, Titanium
Europe, p.12-17, March 1995.

10.

ASM Handbook, Volume 13: Corrosion, 1987.

11.

D.C. Agarwal & Michael Eckhardt: Nickel alloys and newer super-austenitic alloys contributions
in the CPI and Petrochemical Industries, Paper No. 06233, Corrosion 2006.

12.

Paul Crook: The corrosion-resistant nickel alloys, Haynes International, Inc., USA, Achema
2006.

13.

John W Oldfield: Corrosion Initiation and Propagation of Nickel Base Alloys in Severe Seawater
Applications, Paper No. 266, Corrosion 95.

14.

Bla Leffler: Stainless stainless steels and their properties, Avesta Sheffield.

TABLE 1
CHEMICAL COMPOSITION OF TESTED NICKEL-BASE MATERIALS
UNS No.

Alloy

Ni

Cr

Mo

Fe

Bal.

20-22.5

12.5-14.5

2-6

2.5 max. 2.5-3.5

N10276 Alloy C-276 Bal. 14.5-16.5

15-17

4-7

2.5 max.

N06200 Alloy C-2000 Bal.

22-24

15-17

3 max.

2 max.

N06059 Alloy 59

22-24

15-16.5

N06022 Alloy C-22

Bal.

Co

Cu

Others

Mn, Si, V, C

3-4.5

0.5 max.

Mn, Si, V, C

1.3-1.9

Mn, S, Si, Al

1.5 max. 0.3 max.

0.5 max. Mn, S, Si, Al

TABLE 2
CHEMICAL COMPOSITION OF TESTED STAINLESS STEEL MATERIALS
UNS No.

Alloy

Fe

Cr

Ni

Mo

Cu

S31254

254 SMO Bal. 19.5-20.5 17.5-18.5 6-6.5 0.18-0.22 0.02 0.50-1.0

S31277

27-7Mo

Bal.

20.5-23

26-28

6.5-8

N08031

Alloy 31

Bal.

26-28

30-32

6-7

0.3-0.4

0.02

0.15-0.25 0.02

0.5-1.5
1-1.4

Others

PRE
42

Mn

47
48

FIGURE 1 - General principle of a compact plate heat exchanger (CHE).

Test unit
Seawater outlet

Seawater inlet

Hypochlorite dosing

FIGURE 2 - General sketch of test loop configuration.

FIGURE 3 - Appearance of the CHE test unit.

~ 50 x

FIGURE 4 - Cross-section of plate contact point N06022.

The line indicates the original appearance of the plate.

10

~ 50 x

FIGURE 5 - N06200. Example of crevice corrosion initiation in a plate contact point.

~9x

FIGURE 6 - S31254 was subject to penetrating corrosion attacks

after 3 months test in non-chlorinated seawater at 60C (140F).

11

FIGURE 7 - N08031. Penetrating corrosion attacks in the gasket groove area

at 50C (122F) in chlorinated seawater, 1 ppm FAC continuously .

12