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Summary
In drinking water systems, the main stainless steel grades used are the standard austenitic
stainless steel grades 4307 (304L) and 4404 (316L), with the grade selection depending on the
chloride and chlorine levels in the water. The lean duplex grades LDX 2101® and LDX 2404®
provides attractive alternatives, with a more stable price and higher strength level, but there is little
available data on their use in drinking water systems.
The European Drinking Water Directive sets a maximum limit of 250 ppm (mg/L) for chlorides in
drinking water but does not contain guidelines for chlorine. Drinking water is normally treated to give
a residual level of 0.2 to 0.5 ppm of chlorine to kill bacteria, but the actual concentrations added are
usually higher. The WHO drinking water standard states that 2-3 ppm chlorine should be added to
water in order to gain a satisfactory disinfection and adequate residual concentration. For a more
effective disinfection the residual amount of free chlorine should exceed 0.5 ppm after at least 30
minutes of contact time at a pH value of 8 or less.
The residual chlorine has a significant influence on the corrosion behavior of stainless steels. The
remaining of residual chlorine in drinking water is a major factor leading to the ennoblement of the
natural potential of stainless steel. This oxidizing effect of chlorine may have detrimental
consequences in that stainless steels may suffer from localized corrosion if an inappropriate grade
is used.
The aim was to understand and determine to what extent residual chlorine levels at various chloride
contents will affect the localized corrosion behaviour of the standard austenitic stainless steel
grades 4307 and 4404, also the duplex grades LDX 2101®, LDX 2404® and 2205. A simulated
chlorination system was created in which the specimens were immersed for 30 days at 30C and
50C at chloride levels of 200 ppm and 500 ppm, with residual chlorine levels of 0.2, 0.5 and 1 ppm
at pH 6.5-7.5. The specimens were investigated by visual examination and microscopy.
The duplex grades LDX 2404® and 2205 perform very well in all the chlorinated environments
tested. The lean duplex grade LDX 2101® performed as well as or better than 304L at both 30°C
and 50C. The results also indicated that the presence of a crevice increased the risk for localized
corrosion in a chlorinated environment. This study demonstrates that duplex stainless steels are
good candidates to use in water pipes or water storage tanks.
Keywords: drinking water, chloride, chlorination, total residual chlorine (TRC), localised corrosion,
stainless steel
1 Introduction
Stainless steel use for drinking water applications is increasing in the world. Stainless steels offer
several advantages compared to other materials, such as mild steel, cast iron and copper which
have been used for decades. First of all, stainless steels have generally excellent corrosion
resistance and require little maintenance. There is no need for any protective coating or any
protective system. Correct grade selection and good practice will minimize the risk of any localized
corrosion. Therefore, there is practically no contamination of water in contact with stainless steel, as
has been demonstrated in the investigation [1] shown in Figure 1.
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S. Mameng, R. Pettersson | EUROCORR 2011, STOCKHOLM, SWEDEN
Figure 1: Nickel (Ni) and Chromium (Cr) content of water drawn from stainless steel water systems
in a Scottish hospital [1]
Figure 1 show the leaching values for Cr and Ni were less than 5% of the maximum levels permitted
by the European Drinking Water Directive (50 and 20 g/L respectively) [2]. The low leaching levels
from the use of stainless steel in the drinking water system are clearly of benefit in this situation.
Another point to be considered is the mechanical properties. The good ductility, strength and
weldability enable the use of lightweight structures, for example thin walled tubes. Among the
stainless steels, the duplex materials exhibit much higher mechanical strength than corresponding
austenitic grades as shown in Table 1. Compared to other materials used for applications in the
potable water distribution network, duplex grades allow a reduction in wall thickness and
consequently reduces investment costs. All together stainless steels give a life cycle cost benefit.
Table 1: Minimum mechanical strengths at 20°C of hot rolled plate/cold rolled strip and sheet
according to EN 10088-4 and EN 10028-7 when applicable [3,4,5].
Outokumpu 0.2% Yield Strength Tensile Strength Elongation
EN Designation
steel names MPa MPa %
4301 1.4301 210/230 520/540 45/45
4307 1.4307 200/220 500/520 45/45
Austenitic
4401 1.4401 220/240 520/530 45/40
4404 1.4404 220/241 520/531 45/41
*
LDX 2101® 1.4162 480/530 680/700 30/30
**
Duplex LDX 2404® 1.4662 550/550 750/750 25/25
2205 1.4462 460/500 700/700 25/20
* LDX 2101® is not yet listed in EN 10028-7.
** LDX 2404® is not yet listed in EN 10088-4 or EN 10028-7. Data for LDX 2404® corresponds to the internal standard AM 641.
Two main alloying elements of stainless steels are chromium (Cr) and nickel (Ni). From a general
point of view, chromium improves the pitting corrosion resistance whereas nickel additions are
made for controlling microstructure. Further alloying elements may be added like molybdenum (Mo)
for increasing pitting resistance or nitrogen (N) for improving mechanical properties and resistance
to pit initiation. Depending on the stainless steel composition and chloride content of water, these
materials may be resistant to aqueous corrosion in a wide range of pH at ambient temperature.
Stainless steels ability to resist pitting corrosion may be estimated by calculation of the Pitting
Resistance Equivalent Number (PREN). Equation (1) gives the most frequently employed formula
for PREN calculation.
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S. Mameng, R. Pettersson | EUROCORR 2011, STOCKHOLM, SWEDEN
In drinking water systems, the main stainless steel grades used are the standard austenitic
stainless steel grades 4307 and 4404. The grade selection depends on the chloride levels of the
water and also on the severity of the crevices the materials are exposed to, as shown in Table 2
from the Nickel Development Institute. The chloride content of the water is the most important
parameter because of its influence on localized corrosion, crevice corrosion in particular. The
European Drinking Water Directive sets a maximum limit of 250 ppm (mg/L) for chlorides in drinking
water but does not contain guidelines for chlorine [2].
2 Water Chlorination
Chlorination is a one of many methods that can be used to disinfect water and control bacteria.
Sodium hypochlorite (NaOCl) is the form of chlorine normally use for chlorination process because
it is cheap and easy to dose. When chlorine added to water, it immediately begins to react with
compounds found in the water to give hypochlorous acid (HOCl) and hypochlorite (OCl -). The
remaining amount is called free residual chlorine.
The free residual chlorine is typically measured in drinking water disinfection systems to find if the
water contains enough disinfectant. Typical levels of free chlorine in drinking water are 0.2-0.5 ppm
[7], but the actual concentrations added are usually higher. The WHO drinking water standard
states that 2-3 ppm chlorine should be added to water in order to attain a satisfactory disinfection
and maintain residual concentration [8]. The maximum amount of chlorine one can use is 5 ppm.
For effective disinfection the residual amount of free chlorine should exceed 0.5 ppm after at least
30 minutes of contact time at a pH value of 8 or less.
The residual chlorine has a significant influence on the corrosion behaviour of stainless steels. The
remaining residual chlorine in drinking water is thought to be a major factor leading to the
ennoblement of the natural potential of stainless steel. This oxidizing effect of chlorine may have
detrimental consequences and stainless steels may suffer from localized corrosion if an
inappropriate grade is used.
This work was conducted to understand and determine to what extent total residual chlorine levels
at various chloride contents will affect the pitting and crevice corrosion behaviour of the standard
austenitic stainless steel grades 4307 and 4404, also the duplex grades LDX 2101®, LDX 2404®
and 2205. The recently introduced duplex grades LDX 2101 ® and LDX 2404® provide an attractive
alternative, with a more stable price and higher strength level, but there is little available data on
their use in drinking water systems.
3.1 Materials
The material used in this study are 4307, 4404, LDX 2101 ®, LDX 2404® and 2205 which were all
tested as plain (sheet), welded and creviced samples. The surface finish, thickness, PREN values
and the chemical composition of these materials are reported in Table 3.
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S. Mameng, R. Pettersson | EUROCORR 2011, STOCKHOLM, SWEDEN
Table 3: Steel grades, surface finish, thickness, PREN values and the chemical composition for
materials used in long term chlorination.
2A 2B
Figure 2: Coupons of plain (sheet), welded and crevice specimens used for long term testing
The welded samples were obtained by tungsten inert gas welding (TIG). The welding was done with
filler material and welding conditions as specified in Table 4 and Table 5 below. This welding
process is often used for water applications. All samples have the same thickness of 3 mm. Weld
samples were pickled in mixed acid (3M HNO3 and 3M HF).
Chloride (Cl-) containing electrolytes with various total residual chlorine (TRC) levels, at pH 6.5-7.5,
were prepared from distilled water. Chloride ions were added to the level of 200 ppm and 500 ppm
as sodium chloride (NaCl). The solutions were dosed with a stock solution containing 1000 ppm of
sodium hypochlorite to obtain various predetermined total residual chlorine concentrations.
Total residual chlorine (TRC) is defined as the sum of hypochlorous acid (HClO) and hypochlorite
ion (ClO-) concentrations.The amount of residual chlorine was measured with a colorimeter using
the diethyl-p-phenylene diamine (DPD) method [10]. Three total residual chlorine concentrations
were investigated that correspond to the residual concentration typically used for water disinfection
treatments: 0.2, 0.5 and 1 ppm.
The open circuit potential (OCP) was monitored for 30 days in the test solutions with the different
residual chlorine levels and a temperature of 30C or 50C. The chlorine was dosed once every 5-7
days to maintain the residual chlorine level. After testing the specimens were examined and the
depth of maximum attack was measured with a light optical microscope. A depth exceeding 0.025
mm was defined as localised corrosion.
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S. Mameng, R. Pettersson | EUROCORR 2011, STOCKHOLM, SWEDEN
The addition of sodium hypochlorite gave a strong increase in the open circuit potential. After a
certain time, typically10-24 hours the potential stabilised and the OCPMax could be measured as
shown in Figure 3. The result shows that OCPMax increases with TRC level because the oxidising
power of the solution increases, Table 6.
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S. Mameng, R. Pettersson | EUROCORR 2011, STOCKHOLM, SWEDEN
Table 6: Average OCPMax of five different steel grades in water containing chloride and total
residual chlorine at 30C and 50°C
The OCPMax after chlorination compared to the situation before chlorination is shown in Figure 4.
The increase in OCP was about 200 mVSCE for 0.2 ppm TRC, about 300 mVSCE for 0.5 ppm TRC and
about 500 mVSCE for 1 ppm TRC. This indicates that even at low TRC concentrations the open circuit
potential increases.
Figure 5: Corrosion potential change of TIG Figure 6: Corrosion potential change of TIG welded
welded specimens of 4307, LDX2101® and and crevice specimen for 4307 and 2205 in 200
2205 in 500ppm chloride and 1 ppm TRC at ppm chloride and 1 ppm TRC at 30C.
50C showing the potential drop associated with
the onset of pitting corrosion.
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S. Mameng, R. Pettersson | EUROCORR 2011, STOCKHOLM, SWEDEN
Pitting corrosion
on the weld
Crevice corrosion
The results show that the alloying elements influence the localised corrosion resistance of stainless
steel. For the austenitic steels, the corrosion resistance for molybdenum (Mo) containing grade
(4404) is higher than for the molybdenum (Mo) free grade (4307). A higher chromium (Cr) level in
combination with nitrogen (N) addition has the same positive influence for duplex grades. The
results also indicated that the presence of a crevice increases the risk for localized corrosion in
chlorinated environments. Special attention should be taken, to avoid crevices in construction, since
residual chlorine solution can remain in crevice areas and cause corrosion.
Table 7: Summary of visible pitting and crevice corrosion in this investigation (Red cells =corrosion,
Green cell = no corrosion and Black cell = not tested)
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S. Mameng, R. Pettersson | EUROCORR 2011, STOCKHOLM, SWEDEN
Figure 8: Engineering diagram indicating the maximum temperatures and chloride concentration
allowed in slightly chlorinated (<1 mg/L) drinking water for 4307 and 4404 [11].
A summary of chlorination limits for different grades from this investigation are shown in Table 8.
Table 8: Chlorination limits which did not cause corrosion in the 30 days immersion tests for
different grades depending on chloride content
Test condition TRC limits (ppm) for different grades depending on chloride content
Temp. Chloride 4307 4404 LDX 2101® LDX 2404® 2205
(C) (ppm) P W C P W C P W C P W C P W C
30 200 0,5 0,5 <0.2 1 1 1 1 1 <0.2 1 1 1 1 1 1
30 500 0,5 0,5 (<0.2) 1 1 0,2 0,5 0,5 <0.2 1 1 1 1 1 1
50 200 0,5 0,5 0,2 1 1 0,5 0,5 0,5 0,2 1 1 1 1 1 1
50 500 0,5 0,2 (<0.2) 0,5 0,5 0,2 0,5 0,2 <0.2 1 1 1 1 1 1
P = plain (sheet) sample; W = welded sample; C = creviced sample; TRC = total residual chlorine; NT= not tested
It is important that a material is not exposed to excessive levels of residual chlorine. For effective
disinfection the residual chlorine should exceed 0.5 ppm after at least 30 minutes of contact time
[8]. During practical operation, the chloride content will most probably be lower than during this test.
Thus, there is a good chance that the 4307, LDX 2101® and 4404 can be used successfully for
normal service in water piping systems as long as problematic crevices can be avoided. In doubtful
cases upgrading to LDX 2404® or 2205 may be advisable.
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S. Mameng, R. Pettersson | EUROCORR 2011, STOCKHOLM, SWEDEN
5 Conclusion
• In long-term (30 days) immersion tests, the highest alloyed duplex grades 2205 and LDX
2404® performed very well in the chlorinated environments tested (200 or 500 ppm chloride,
30C or 50C). No pitting, crevice corrosion or weld attack was seen in any of the
environments for these grades.
• The lean duplex grade LDX 2101® performed as well as or better than 4307 (304L) at all
conditions tested. In the pitting test it performed as well as 4404 (316L) in 200 ppm chloride
at 30C.
• Chlorine solution with significant residual chlorine concentrations can remain in crevice
areas and cause corrosion, and therefore special attention should be taken in construction.
• The lean duplex steel LDX 2101® is a good candidate for water piping systems and tanks,
when the water is mildly chlorinated. In more severe condition the higher alloyed LDX
2404® or 2205 are more suitable.
• Material selection guidelines depending on chloride content, chlorine dosage and
temperature are shown in Table 9 and Table 10 below. In order to ensure good
performance deposits and surface contamination should be avoided.
Table 9: Summarised results of 30 day tests in chlorinated solutions containing 200 ppm chloride at
30°C or 50°C.
BM Weld Crevice
304L 316L 304L 316L (304L) 316L
LDX 2101® LDX 2404® LDX 2101® LDX 2404® (LDX 2101®) LDX 2404®
1
2205 2205 2205
304L 316L 304L 316L 304L 316L
0.5
50
LDX 2101® LDX 2404® LDX 2101® (LDX 2404®) LDX 2101® (LDX 2404®)
2205 2205 (2205)
304L 316L 304L 316L 304L 316L
Temperature (°C)
0.2
Chlorine (ppm)
LDX 2101® LDX 2404® LDX 2101® (LDX 2404®) LDX 2101® (LDX 2404®)
2205 2205 (2205)
LDX 2101® (LDX 2404®) (LDX 2101®) (LDX 2404®) LDX 2101® (LDX 2404®)
2205 (2205) (2205)
304L 316L (304L) (316L) 304L (316L)
0.2
LDX 2101® (LDX 2404®) (LDX 2101®) (LDX 2404®) LDX 2101® (LDX 2404®)
2205 (2205) (2205)
200 ppm Chloride
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S. Mameng, R. Pettersson | EUROCORR 2011, STOCKHOLM, SWEDEN
Table 10: Summarised results of 30 day tests in chlorinated solutions containing 500 ppm chloride
at 30°C or 50°C.
BM Weld Crevice
304L 316L 304L 316L (304L) 316L
LDX 2101® LDX 2404® LDX 2101® LDX 2404® (LDX 2101®) LDX 2404®
1
2205 2205 2205
304L 316L 304L 316L (304L) 316L
0.5
50
LDX 2101® LDX 2404® LDX 2101® (LDX 2404®) (LDX 2101®) (LDX 2404®)
2205 (2205) (2205)
304L 316L 304L 316L 304L 316L
Temperature (°C)
0.2
Chlorine (ppm)
LDX 2101® LDX 2404® LDX 2101® (LDX 2404®) LDX 2101® (LDX 2404®)
2205 (2205) (2205)
1
2205 2205 2205
304L 316L 304L (316L) (304L) 316L
0.5
30
LDX 2101® (LDX 2404®) LDX 2101® (LDX 2404®) LDX 2101® (LDX 2404®)
2205 (2205) 2205
304L 316L 304L (316L) 304L (316L)
0.2
LDX 2101® (LDX 2404®) LDX 2101® (LDX 2404®) LDX 2101® (LDX 2404®)
2205 (2205) 2205
500 ppm Chloride
6 References
[1]. C.A. Powell and W.Strassburg, Stainless Steel for Potable Water Service, 2 nd European
Stainless Steel Congress, Düsseldorf, 1996.
[2]. European Drinking Water Council Directive 98/83/EC, Nov 1998.
[3]. Outokumpu data sheet, Standard Cr-Ni stainless steel.
[4]. Outokumpu data sheet, Standard Cr-Ni-Mo stainless steel.
[5]. Outokumpu data sheet, Duplex stainless steel
[6]. Peter Culter, Stainless steel and drinking water around the word, Nickel Development institute
(NiDi).
[7]. The chlorine institute.INC, Chlorine effect on health and the environment, 3 th Edition-Nov.1999.
[8]. Guildlines for Drinking Water Quality, 3rd Edition, 2008.
[9]. Avesta Welding handbook, 3rd Edition, Dec 2007.
[10]. Pradyot Patnaik, (1995), Dean’s Analytical Chemistry Handbook, McGraw Hill, New York.
[11]. Outokumpu, Corrosion Handbook, 10th Edition, Nov 2009.
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