A CORROSION MANAGEMENT AND APPLICATIONS ENGINEERING MAGAZINE FROM OUTOKUMPU

Corrosion Properties of
Enhanced Duplex Steel
UNS S32304

2/2015

2/2015 |

Corrosion Properties of Enhanced

Duplex Steel UNS S32304
Lena Wegrelius and Sukanya Hgg Mameng
Outokumpu Stainless AB, Avesta, Sweden

Abstract

Introduction

The enhanced duplex stainless steel S32304 is a recently

developed duplex steel grade with enhanced properties; increased
strength and improved corrosion resistance. The improvement has
been made possible by a combination of modern production
technology and a change of the chemical composition within the
chemical range of the UNS S32304 standard. The enhanced
duplex steel grade S32304 has higher contents of chromium,
molybdenum and nitrogen than the traditional S32304. The PREN
(Pitting Resistance Equivalent) value is guaranteed to be 28,
as compared to only 26 for the standard S32304 grade. The
production process has been verified according to the NORSOK
M-650 framework.
This paper describes the results of corrosion properties in
the terms of localized corrosion testing according to ASTM G48
(in FeCl3) and G150 (in NaCl) and stress corrosion cracking
testing according to G36 (in MgCl2) and G123 (in NaCl). Uniform
corrosion testing in different media is illustrated with the critical
temperatures, evaluated according to the MTI-1 (G157) method.
The enhanced duplex steel S32304 is an excellent choice in
many applications where S32205 is over-specified in regards to
corrosion resistance. The improved properties make the enhanced
S32304 well suited for optimal designs with respect to strength,
reduced maintenance, durability and long-term service. Potential
applications for this grade are within structural design, e.g. in the
oil and gas industry.

The enhanced duplex stainless steel UNS(1) S32304, is a recent

development of the traditional UNS S32304 grade for the offshore
industrys needs. The industry needed a competitive alternative
that would have higher corrosion resistance than S31603 (316L)
and would be stronger than the traditional S32304 grade.
The improvement has been made possible by a combination
of modern production technology and a change of the chemical
composition, still within the chemical range of the UNS S32304
standard. The enhanced duplex steel grade S32304 has higher
contents of chromium, molybdenum and nitrogen than the
traditional S32304. The PREN (Pitting Resistance Equivalent
Number) is guaranteed to be 28, as compared to only 26 for
the traditional S32304 grade. Furthermore, proof strength has
been increased from 400 to 500 MPa for thicknesses up to and
including 13 mm. The production process has been verified
according to the NORSOK M-650 framework [1].
The enhanced duplex steel S32304 is an excellent choice in
many applications where S32205 is over-specified in regards to
corrosion resistance. The improved properties make the enhanced
S32304 well suited for optimal design with respect to strength,
reduced maintenance, durability and long-term service. Potential
applications for this grade are within structural design, e.g.
offshore topside structural components in the oil and gas industry.
Figure 1 illustrates the positioning of the enhanced S32304
grade in relation to other duplex and austenitic stainless steel
grades. The objective of this work was to investigate and document
the corrosion properties of the enhanced duplex grade S32304.
Some welded material was included to illustrate the influence of
microstructure and structural stability on the corrosion resistance.
The result is compared with data from traditional S32304 grade
and the standard austenitic grade S31603.
Strength MPa, Min values, hot rolled coil (ASTM A 240)

Key words: Duplex stainless steel, lean duplex, corrosion

resistance, welding

600

S32750

550

Enhanced S32304

500

S32101

S82441

450

S32205
S34565

S32304

400
350

S31254

300

S31726

250
S30403

200
150

N08904

S31703

10

S31603

20

30

40

50

60

Figure 1 Positioning of the enhanced S32304 grade.

(1)

Unified Numbering System for Metals and Alloys (UNS).

70

80

Critical pitting temperature (C) ASTM G 150

90

100

2/2015 |

Experimental Procedure
Material
The chemical composition of the stainless steel grades included in
this study is given in Table 1. Because a number of different heats
were used for the various tests, the typical compositions are given.
The austenitic stainless steel grade UNS S31603 is includes as
reference. Also included in Table 1 is the Pitting Resistance
Equivalent Number (PREN). PREN is in this study defined as
PREN = %Cr + 3.3(%Mo) + 16(%N).

Corrosion testing
Several corrosion tests were performed to verify the improved
corrosion properties of the enhanced grade S32304. Most of the
tests were performed on 6 8 mm thick un-welded material but
also some tests were performed on 2 mm thick welded material.

Pitting and crevice corrosion testing

The pitting resistance was evaluated using either ASTM(2) G 48 [2]
method E or ASTM G150 [3] and the crevice corrosion resistance
was evaluated using ASTM G48 method F. The G48 methods
involve immersion of the test specimens in 6% FeCl3 + 1% HCl for
24 hours at different temperatures with an increment of 5C for
evaluation of critical pitting temperature (CPT) and critical crevice
temperature (CCT). The specimens were cut to approximate
dimensions of 50 x 25 mm. The material investigated was dry
ground to 120 grit finish including the cut edges. New specimens
and test solutions were used for each test temperature.
The electrochemical ASTM G150 determines the critical pitting
temperature in 1M NaCl solution by a potentiostatic technique
which uses a temperature scan and a flushed port cell (the Avesta
Cell [4]) that eliminates the occurrence of crevice corrosion.
All specimens, except those with weld, were wet ground to 320 grit
at least 18 hours prior corrosion testing.
Pitting potential (Epit) measurements were performed in 1 M
sodium chloride solution at different temperatures ranging from
201C up to 501C. Specimens of size 30 x 30 x t mm were
used and were wet ground to 320 grit at least 18 hours before
testing, then immediately before the experiment cleaned with
ethanol. The flush port cell was used in all the electrochemical
experiments. Polarization measurements were made using a
Solartron 1287 potentiostat. The potential of the working
electrode was measured versus a saturated calomel (SCE) reference
electrode. The auxiliary electrode was platinum (Pt) wire. Dissolved
oxygen was maintained at a low level by bubbling nitrogen through
the sodium chloride solution during the whole test time. Before
each polarization measurement, the open circuit potential (EOCP)

was measured for 10 minutes in the test solution. The polarisation

started at -300 mVSCE and the scan rate was 20 mVmin-1. Epit was
defined at the point where the current exceeds 100 Acm-2 and
remains above this level for at least 1 minute. Duplicate samples
were tested and gave in most cases a difference of <100 mVSCE.
If larger differences were observed, additional measurements were
performed.

Uniform corrosion testing

The uniform corrosion tests were carried out according to MTI(3) -1
test procedure [5] (ASTM G 157 [6]). This involves determination
of the critical temperature, at which the corrosion rate exceeds
0.127 mm/year. Specimens of each steel grade were cut to the
dimension 50 x 20 x t mm. The surfaces were dry ground to 120
grit finish, degreased in acetone. Before testing the specimens were
allowed to passivate in air for at least 18 hours. 600 ml solution
was either cooled or heated to a suitable start temperature and
duplicate specimens were thereafter immersed in the test solution.
Nitrogen was used to deaerate the solutions during the 96 hours
test period.
If one or both of the test specimens had a corrosion rate higher
than 0.127 mm/year the temperature was reduced by 5C during
the next test period, otherwise the temperature was increased
5C, until the critical temperature was reached and evaluated.

Stress corrosion cracking testing

Three different stress corrosion cracking test methods were
performed; ASTM G 36 [7] (MgCl2), ASTM G123 [8] (NaCl) and
in concentrated CaCl2 solution.
U-bend specimens were prepared according to ASTM G30 [9].
Specimens with dimension 127 x 13 mm were cut from sheet
parallel to the rolling direction. All specimens were dry ground to
120 grit. The specimens were stressed using a two-stage method
around a mandrel with 25 mm diameter, and secured with nuts
and bolts. Before the final stressing stage the specimens were
degreased in acetone. The time between the two stressing stages,
and between the final stressing stage and the start of the test,
was kept as short as possible. In the final stage the specimens
were adjusted to a correct U-shape with parallel legs. To maintain
the load tightening bolts made of titanium were used together with
Teflon washers for insulation.
In the first test the U-bend specimens were exposed to 45%
boiling magnesium chloride solution for 24 hours and the
temperature was maintained at 155C.

Cr

Ni

Mo

PREN

UNS S32304 traditional

0.02

0.10

23

4.8

0.3

26

UNS S32304 enhanced

0.02

0.18

23.8

4.3

0.5

28

UNS S31603

0.02

17.2

10.1

2.1

24

Steel grade

Table 1 Typical composition of the tested steel grades [wt%].

ASTM International, 100 Barr Harbor drive, PO Box C700, west Conshohocken, PA 19428-2959, USA.
Trade name.
(3)
Materials Technology Institute of the Chemical Process Industries, Inc., 1215 Fern Ridge parkway, Suite 116, St. Louis, MO 63141-4401, USA.
(2)

2/2015 |

In the second test the U-bend specimens were immersed in

25% boiling sodium chloride solution acidified to pH 1.5 with
phosphoric acid. The boiling point of the solution is expected to
be 106 110C. The exposure time was 1000 hours (~ 6 weeks)
and for each one-week period fresh solution was used.
Finally, in the third test solution with 40% calcium chloride was
prepared and the pH adjusted to 6 using a slurry of calcium oxide.
The U-bend specimens were placed in the solution and the
solution was heated to 100C. Throughout the test period, the
temperature was maintained at 100C and the pH measured
every second day and adjusted to 6 if necessary. The time to
cracking was observed and if cracking occurred before the end
of the test period of 500 hours the test was terminated.
After exposure the specimens were evaluated by visual
inspection and by optical light microscopy.

backing gas was either pure argon or Formier 10 (90% N2 + 10% H2).
All welded specimens were sand blasted and pickled in mix acid of
3.1M nitric acid and 2.8M hydrofluoric acid at 60C for
5 minutes prior corrosion testing.
To investigate the microstructure of the weld and the heat
affected zone, cross sections of the welded specimens were
ground and polished to 3m finish prior to the color etching in
modified Beraha(5) etchant at room temperature.

Results & Discussion

Corrosion properties of base material
Pitting and crevice corrosion

CPT (C)

The results from ferric chloride immersion tests of the base material
evaluated according to ASTM G48 method E and F and the
electrochemical testing in sodium chloride according to ASTM
Welding and microstructure
G150 are illustrated in Figure 2. For the enhanced grade S32304,
To investigate the corrosion properties after welding 2 mm
the ASTM G48 E and F test methods were repeated six and three
enhanced S32304 was mechanized TIG(4) welded using filler metal
times respectively. For the other grades, typical values are given.
EN ISO: 22 9 3 N and thereafter tested according to ASTM
> 90G150, > 90 >As
90 can be seen in the figure, the enhanced S32304 grade
critical pitting temperature in 1M NaCl. Two shielding gas types
performs significantly better than the traditional S32304 in all
were used in the test; pure argon and argon with 2% nitrogen. The
three tests. In fact, the enhanced S32304 grade was the only
grade were it was possible to get a positive
CCT value. For the other two grades, traditional
40
S32304 and S31603, the CCT values were
S32304 enhanced
S31603
S32304
not possible to measure without cooling the
35
solution below zero. This is also in agreement
30
with the fact that the enhanced grade
S32304 has a higher alloying content of
25
chromium, molybdenum and nitrogen than
the traditional grade S32304.
20
The result from the pitting potential
15
measurements is illustrated in Figure 3. At
10
all investigated temperatures, the enhanced
S32304 gave the highest break through
5
potential in comparison to the other two
0
investigated materials. In the tests performed
G48 E
G48 F
G150
at 20 and 30C the enhanced S32304 was
passive, without pitting, up to the transpasFigure 2 Critical pitting temperatures according to ASTM G 48 E and ASTM G
sive
region while the traditional S32304
150 respectively. Critical crevice temperature according to ASTM G 48 F.
and S31603 suffered from pitting corrosion
and experienced pitting potentials at all test
temperatures.
1,4
S31603

Uniform corrosion

S32304 enhanced

S32304

Epit, V (SCE)

1,2

The evaluated critical temperatures in the

uniform corrosion test are presented in
Table 2. The enhanced duplex stainless
steel grade S32304 shows good result;
equal or slightly better than the traditional
S32304 in the tested solutions (the
exception is WPA(6)-1, where the result for
the traditional grade was somewhat better
than for the enhanced S32304).

1
0,8
0,6
0,4
0,2
0
20

30

40
Temperature (C)

Figure 3 Break through potentials versus temperature.

(4)
( )
(5)

Tungsten Inert-Gas arc welding (TIG).

Trade name.
50 ml HCl + 100 ml H2O, 1 g/100 ml K2S2O5.

50

2/2015 |

Stress corrosion cracking

45
Critical pitting temperature (CPT, C)

In Table 3 the result from the stress corrosion cracking testing

is summarized. All investigated steel grades failed in the most
aggressive test, boiling magnesium chloride solution. In the two
other tests, both the traditional and the enhanced S32304
performed well with no signs of cracking while the standard
austenitic steel grade S31603 failed due to stress corrosion
cracking.

Properties of welded material

The critical pitting temperature according to ASTM G150 was
determined on welded and pickled specimens of enhanced grade
S32304. For comparison, the CPT was determined for the base
material of the same heat as the welded specimens. The result is
illustrated in Figure 4. By using argon based shielding gas, the CPT
was decreased significantly most probably due to nitrogen
depletion.
The microstructure of the TIG welded specimens shows
somewhat higher austenite content when nitrogen was present in
the shielding and backing gas compared to pure argon, as shown
in Figure 5 a and b. This is also numerically shown in Table 4 which
exemplifies the beneficial effect of using nitrogen based shielding
and backing gas when TIG welding duplex stainless steels,
especially higher nitrogen alloyed grades like the enhanced
S32304 grade.
The heat affected zone, HAZ, is relatively narrow and shows a
level of ferrite close to that of the weld metal and even lower than
the weld metal for argon based gas.

S32304 enhanced

40
35
30
25
20
15
10
5
0
Base material

Argon

Nitrogen

Figure 4 Critical pitting temperatures according to ASTM G 150 on welded

specimens of enhanced S32304.
a)

b)

Figure 5 a) Argon based gas protection. b) Nitrogen based gas protection

HCl

H2SO4

H2SO4

H3PO4

WPA 1(7)

HNO3

NaOH

HCOOH

Conc. %wt

10

96

85

75

65

50

50

S32304 traditional

70

70

35

90

60

90

100

85

S32304 enhanced

75p

75

40

90

55p

95

105

90

Test solution

(8)

Table 2 Critical temperatures in different solutions according to the MTI-1 procedure.

ASTM G 36, 45% MgCl2

ASTM G123, 25% NaCl, pH 1.5

40% CaCl2, pH 6

U-bend

U-bend

U-bend

Test method
Tested

Failed

Tested

Failed

Tested

Failed

S32304 traditional

S32304 enhanced

S31603

Table 3 Test result for the stress corrosion cracking (SCC) testing.

ID

Shielding
gas

Backing
gas

Rm, MPa

Fracture
location

Bend test,
4xt, 180

G150,
CPT, C

Ferrite content

WM(9)

HAZ(10)

BM(11)

Ar

Ar

Ar

742 12

WM

4 OK

71 4

68 3

45 2

32 3.4

N2

Ar + 2%N2

90% N2
+ 10% H2

754 11

WM

4 OK

62 4

67 5

46 3

41 1.3

Table 4 Properties of enhanced S32304 welded with different shielding and backing gas.
(6)
(7)
(8)

Wet Phosphoric Acid (WPA)

WPA-1 = 75% H3PO4, 0,2% Cl-, 0,5% F-, 4% H2SO4, 0,3% Fe2O3, 0,2% Al2O3, 0,1% SiO2, 0,2% CaO, 0,7% MgO
p = pitting corrosion.

WM = weld metal.
HAZ = heat affected zone.
(11)
BM = base metal.
(9)

(10)

2/2015 |

Conclusions

References

In this study the corrosion properties of enhanced duplex grade

S32304 have been investigated by different corrosion test methods in
order to evaluate the performance under different process conditions
and environments. The result from these tests shows that:

[1] NORSOK STANDARD M-650:2011, Qualification of

manufacturers of special materials.

The increased alloying content of chromium, molybdenum and

nitrogen in the enhanced duplex grade S32304 has a significant
beneficial effect on the pitting and crevice corrosion resistance
compared to the traditional S32304 grade.
The resistance to uniform corrosion is equal or slightly better
for the enhanced S32304 than for the traditional S32304.
The resistance to stress corrosion cracking is equal for the
enhanced S32304 and the traditional S32304. Both the
enhanced and the traditional S32304 grades have significantly
higher resistance to stress corrosion cracking (SCC) than the
austenitic grade S31603.
It is beneficial to use nitrogen based shielding and backing
gas when TIG welding nitrogen alloyed duplex grades like the
enhanced S32304.
The enhanced duplex grade S32304 is an excellent choice in
many applications where there is a need of higher corrosion
resistance and higher mechanical strength than what the
traditional S32304 and the standard austenitic grade S31603
can offer.

[2] ASTM G48 Standard Test Methods for Pitting and Crevice
Corrosion Resistance of Stainless Steels and Related Alloys
by Use of Ferric Chloride Solution.
[3] ASTM G150 Standard Test Method for Electrochemical
Critical Pitting Temperature Testing of Stainless Steels.
[4] R. Qvarfort, New Electrochemical Cell for Pitting Corrosion
Testing, Corrosion Science, Vol 28, No 2, 1988,
pp. 135 140.
[5] MTI-1 Corrosion resistance in Selected Media,
MTI Publication No. 46, (1995).
[6] ASTM G157 Standard Guide for Evaluating Corrosion
Properties of Wrought Iron- and Nickel-Based Corrosion
Resistant Alloys for chemical Process Industries.
[7] ASTM G36 Standard Practice for Evaluating StressCorrosion-Cracking Resistance of Metals and Alloys in
a Boiling Magnesium Chloride Solution.
[8] ASTM G123 Standard test Method for Evaluating StressCorrosion Cracking of Stainless Alloys with Different Nickel
Content in Boiling Acidified Sodium Chloride Solution.
9] ASTM G30 Standard Practice for Making and Using U-Bend
Stress-Corrosion Test Specimens.

Acknowledgements
Jan Bjrk, Hans-Erik Peth, Marie Almn and Mikael Schnning are
greatly acknowledged for carrying out the corrosion experiments.

Reproduced with permission from NACE International, Houston, TX.

All rights reserved. Paper C2013-5897 presented at CORROSION/2015, Dallas, TX.
NACE International 2015.

1572EN-GB, Art 58, 06, 15.

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