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A CORROSION MANAGEMENT AND APPLICATIONS ENGINEERING MAGAZINE FROM OUTOKUMPU 1/2014

Corrosion performance of welds


in duplex, superduplex and lean
duplex stainless steels
1/2014 | 2

Corrosion performance of welds


in duplex, superduplex and lean
duplex stainless steels
Rachel Pettersson, Avesta Research Centre, Outokumpu Stainless AB, Avesta, Sweden

Mikael Johansson, Avesta Research Centre, Outokumpu Stainless AB, Avesta, Sweden

Elin M. Westin, Avesta Research Centre, Outokumpu Stainless AB, Avesta, Sweden
Now at: Böhler Schweißtechnik GmbH Austria, Kapfenberg, Austria

Abstract modified in terms of composition by addition of filler metal, and


the surrounding heat affected zone in which there is an imposed
To achieve good corrosion resistance in a weld is much more heating and cooling cycle on the base material. An indication of
challenging than for plate or sheet material, which has undergone the transformations which can occur is shown in the equilibrium
controlled rolling, heat treatment and pickling processes in the diagram in Figure 1. On solidification from the melt, ferrite is
steel mill. The choice of weld procedure and parameters, filler formed first, then some of this ferrite transforms to austenite in
metal and shielding gas all play important roles. For duplex and the solid state. In practice what this means for welding is that an
lean duplex grades it is essential to ensure that an adequate almost fully ferritic weld can be produced if the cooling is very fast
amount of austenite is formed in the weld metal and heat affected so that there is insufficient time for the transformation to austenite
zone, in order to fulfil requirements in terms of austenite-ferrite to occur. This has the further drawback that nitrogen, which
phase balance, but also to avoid the precipitation of detrimental partitions preferentially to the austenite phase, may become
phases such as intermetallics and nitrides. In addition, the trapped in the ferrite where it forms nitrides. This may typically
importance of good post-weld cleaning to ensure good corrosion occur if the heat input is low and is typically encountered for laser
properties cannot be over-emphasised. welds in which the melted volume is small and cools rapidly due to
This paper focuses on a number of different examples of pitting heat loss to the surrounding material. Slower cooling allows time
corrosion of welds in the duplex grades UNS S32101, S32304, for an adequate amount of austenite to form but should not be so
S32205, S82441 and S32750. These illustrate the role of slow as to promote the precipitation of intermetallic phases such
microstructure control to attain good corrosion performance. as sigma phase or, at lower temperatures, nitrides and carbides.
The effect of residual weld oxides or heat tint in degrading the
corrosion performance is also explored, together with evaluation
of the degree to which the corrosion resistance can be restored Melt
1.0
by the use of appropriate pickling processes.
0.9
0.8 Austenite Ferrite
Key words: Stainless, duplex, weld, corrosion, oxide
0.7
Phase fraction (NP°)

Introduction 0.6
0.5
Duplex stainless steels combine a number of attractive features. 0.4 Sigma phase
The two phase microstructure, with approximately equal amounts 0.3
of austenite and ferrite, imparts a higher strength than the
0.2
corresponding austenitic grades and a good resistance to stress
0.1 Nitrides, carbides
corrosion cracking. The lower nickel contents of duplex grades,
typically in the range 1 – 7% compared with 8 – 25 % in the 0.0
500 1000 1500
austenitic grades also gives cost advantages and better price
Temperature (°C)
stability in times of nickel price volatility. In the steel mill, the
duplex stainless steels are produced by a very well controlled Figure 1 Equilibrium phases in a 22Cr duplex stainless steel as a function of
process of rolling, annealing and pickling in order to impart the temperature, calculation using ThermoCalc software with the TCFE5 database.
optimal properties to the material, whether it be as thick plate,
pipe, tube, precision strip or bar. The microstructural issues to be faced when welding duplex
However, the vast majority of applications require welding, stainless steels are thus multiple and only when a satisfactory
which introduces the metallurgical challenges that heating should microstructure is attained will adequate corrosion properties be
not give rise to undesirable phase changes and that a favorable achieved. Having said that, however, there is a certain degree of
structure must be reformed in a matter of seconds after melting. tolerance to the presence of minor amounts of precipitated
This applies both to the weld metal, which is melted and can be phases before the corrosion performance is affected.
1/2014 | 3

Materials Equivalent (PREN) values. This is here defined as PREN = % Cr +


3.3 (% Mo) + 16 (% N) and is a rough predictor of the localized
The materials investigated in this work were five duplex stainless corrosion resistance for a stainless steel in the perfectly annealed
steels spanning a wide range of alloying levels and thus corrosion state with a good surface finish.
resistance. Because a number of different heats were used for The focus of the present work is on the corrosion performance
the various welds, the typical compositions are given in Table 1. of sensitised materials and welds. For details of the welding
All materials were in the mill annealed + pickled condition with 2B processes per se reference is made to the quoted data sources.
or 2E surfaces. Also included in Table 1 are the Pitting Resistance

UNS EN Cr Ni Mo Mn N PREN

S32101 1.4162 21.5 1.5 0.3 5 0.22 26.0


S32304 1.4362 23 4.8 0.3 1 0.1 25.6
S82441 1.4662 24 3.6 1.6 3 0.27 33.6
S32205 1.4462 22 5.7 3.1 1 0.17 35.0
S32750 1.4410 25 7 4 1 0.27 42.5

Table 1 Typical compositions of the duplex stainless steels alloys investigated

Experimental Results & Discussion


Critical pitting temperatures were evaluated using either ASTM Critical pitting and crevice corrosion temperatures for the duplex
G48E or ASTM G150 and critical crevice corrosion temperatures base materials are shown in Figure 2. Good correspondence is
using ASTM G48F. The G48 methods involve immersion testing in actually seen between the G48E and G150 CPT values, although
which separate specimens are exposed to 6 % FeCl3 + 1 % HCl for the former are a few degrees lower and the difference becomes
a period of 24 hours at different temperatures. The disadvantage more pronounced at higher alloying levels. The CPT for the lean
of using these method for welds is that both top and root surfaces duplex S32101 is 15 °C in G48E and in the range 15 – 20 °C in
are exposed during the test, so no differentiation can be made G150, while the corresponding temperatures for the highest
between the two, also that the cut edges of the specimen are alloyed S32750 were 65 °C for G48E and 80 – 85 °C for G150.
exposed. This may be considered unrealistic since such cross-sec- The two can never be used interchangeably.
tions are seldom exposed to a corrosive medium in any actual
application. The G48 immersion testing is also a fairly rough
100
evaluation method, since steps of 5 °C are used according to the
CPT G48E CCT G48F
standard and some scatter is also seen between duplicates.
80
The electrochemical ASTM G150 method allows only a small
Critical temperature (°C)

area, delineated by a water-flushed filter paper, to be in contact


with the test solution of 1 M NaCl. An applied potential of +700 60
mVSCE is imposed then the temperature increased by 1 °C /minute
from 0 °C until an irreversible current increase indicates the onset 40
of pitting corrosion. The drawback with this method is that it
requires a close tolerance between the specimen holder and the 20
area to be tested, otherwise leakage will occur, so special seals
were prepared for testing over the raised weld reinforcement. In
0
addition, it was found that the presence of weld oxides frequently S32101 S32304 S82441 S32205 S32750
caused the measurement to terminate shortly after starting. The
reason was that dissolution of the oxide occurred, giving rise to 100

an increase in measured current without any actual pitting Normal range CPT G150
Critical pitting temperature (°C)

corrosion. In some cases measurements were made in a more 80


dilute solution of 0.1 M NaCl, which increased the CPT by around
5 – 10 °C. All measurements were made as at least duplicates, 60
and the scatter between measurements was typically 1 – 3 °C.
40

20

0
S32101 S32304 S82441 S32205 S32750

Figure 2 Typical critical temperatures for pitting and crevice corrosion of base
metal of different duplex base materials
1/2014 | 4

If duplex stainless steels are subject to slow cooling, as may occur the superduplex S32750, with an appreciable decrease occurring
in conjunction with welding with a very high heat input, or after 10 minutes at this temperature. Scatter bands have been
inappropriate heat treatment in the temperature range omitted from the figure for clarity, but are detailed in [1]. The
300 – 1000 °C (300 – 800 °C for the leaner duplex grades) grades S32304 and S32101 are largely insensitive to heat
microstructural changes, including precipitation of secondary treatment in this temperature range, because their leaner alloying
phases and 475 °C embrittlement, can occur. This is illustrated in concept means that they are remarkably resistant to precipitation
Figure 3 which includes typical microstructures after longer heat of intermetallic phases. However, they do show some decrease in
treatment times. The effect of holding times of 1, 10 or 30 CPT as a result of holding times at 700 °C, where precipitation is
minutes at either 850 °C or 700 °C on pitting corrosion resistance dominated by nitrides and carbides which can form in the phase
is shown in Figure 4. This indicates that a slight drop in CPT occurs boundaries.
after only 1 minute at 850 °C for the standard duplex S32205 and

11000
S32750
1000

900 Intermetallics
S32205 S32101
Temperature (°C)

800
Carbides
& nitrides
700 S32304

600

500
Spinodal
”475 C”
400 embrittlement

300
0.01 0.1 1 10 100 1000
(36s) (6 min) Time (h)

Figure 3 Precipitation kinetics for duplex grades evaluated as the conditions required to give a 50 % reduction in impact toughness, and microstructures illustrating
intermetallic phases, predominantly sigma phase, and carbides/nitrides

100 100
700 °C 850 °C
90 S32750 90 S32750

80 80

70 70
S32205 S32205
SensitisedCPT (°C)

SensitisedCPT (°C)

60 60
0.1 M NaCl 0.1 M NaCl
50 50

40 S32304 40 S32304
S32101 S32101
30 30

20 20

10 10
1 min 10 min 30 min 1 min 10 min 30 min
0 0
0 20 40 60 80 100 0 20 40 60 80 100

Base metal CPT (°C) Base metal CPT (°C)

Figure 4 Effect of holding time at 700 °C or 850 °C in decreasing the CPT compared to that of the base material. 700 °C is the more detrimental temperature
for the lean grades S32101 and S32304 while 850 °C has a larger influence for the standards S32205 or the superduplex S32750
1/2014 | 5

In a welded structure, as opposed to a base material which has


been sensitized to provoke the type of precipitation which can
occur in association with welding, the basic phase morphology is
also altered. Since the weld is fully ferritic on solidification from the
melt, austenite is reformed at the ferrite grain boundaries and as
Widmanstätten austenite in crystallographic orientations within the
ferrite grains, as illustrated in Figure 5. There is a difference in
composition between the austenite and ferrite phases: the former
is enriched in nickel and nitrogen and the latter in chromium and
molybdenum, and this means that there is usually some difference
in corrosion resistance between them. This is also illustrated in
Figure 5, in which it is seen that pitting has preferentially occurred
within the ferrite phase.
Results from a series of CPT measurements on GTA welds in
the five duplex grades are shown in Figure 6, based on data taken Figure 5 Typical pitting in a 22Cr duplex weld, showing how ferrite phase is
from [3, 4]. This shows a number of interesting trends. Firstly, attacked while austenite remains more resistant [2].
the as-welded CPT is between 20 and 40 °C below that of the
corresponding base material, with the result that no as-welded
CPT can be determined for the lean duplex grades S32101 and
S32304. The larger drop is seen when argon is used as a shielding 100 S32705
and backing gas, but this can be mitigated by using nitrogen- N2 (Pickled)
containing shielding and backing gases. The primary reason is 90
N2 (as-welded)
that nitrogen per se improves pitting corrosion (as seen in the 80 Ar (Pickled)
PREN formula) and promotes reformation of austenite to give a Ar (as-welded)
70 S32205
more advantageous phase balance. However, pickling the welds
to remove the very slight amount of weld oxide can almost restore 60 S82441
Weld CPT (°C)

the CPT to the same level as that of the unwelded base material,
50
if nitrogen shielding is employed.
An even more demanding welding process is spot welding, 40 S32304
because the low heat input and thus rapid cooling can give a very S32101
30
ferritic weld. Figure 7 using data from [5] shows how a drop of
around 15 °C in CPT occurs as a result of resistance spot welding 20
thin sheets of duplex steels. In the case of the lean duplex 10
S32101, however, this could be restored to a similar level as the
base material by the use of a protective argon atmosphere to 0
0 20 40 60 80 100
minimize the oxidation of the spot weld. This was particularly
Base metal CPT (°C)
notable since the weld microstructure was far from optimal, with a
high ferrite content of 75 – 85 % and some nitrides present in the
Figure 6 Critical pitting corrosion temperatures according to ASTM G150 for
microstructure. The austenite formation was somewhat lower for the root side of single-side GTA welds on 1 mm material with argon as both
the other two duplex grades, S32304 and S2205, due to the lower shielding and backing gas or with Ar + 2 % N2 as shielding gas and 90 % N2 +
nitrogen contents in these grades. 10 % H2 as backing gas, based on data from [3,4].

100
Shielding gas No shielding
Visible oxide
90
Shielding oxide
80
S32205
70
Spot weld CPT (°C)

60

50 S32304

40

30
S32101
20

10

0
0 20 40 60 80 100

Base metal CPT (°C)

Figure 7 ASTM G150 critical pitting temperature for spot welds in three duplex grades. The beneficial effect of using a shielding gas is apparent for S32101 and
gives a CPT on a par with the base material, in spite of the presence of nitrides in the microstructure, based on data from [5].
1/2014 | 6

The corrosion performance of a number of welds in the lean duplex composition. Adding nitrogen via the shielding gas could have a
grade S32101 are shown in Figure 8, based on data from [6,7]. In beneficial effect on the weld microstructure, as is illustrated in the
each case the base material CPT is given as a reference point, this microstructures, but for the autogenous GTA welds was found to
shows some variation because of the different surfaces and have only a minor influence on the CPT, increasing it from 15 to
product forms tested. All welds were pickled prior to corrosion 17 °C. Even most laser welds showed acceptable CPT values,
testing, attempts to test the GTA welds with residual weld oxides above the normally specified minimum of 15 °C for base material.
caused the CPT measurement to terminate just after the starting The exceptions were the fiber laser weld in 2 mm material and the
temperature of 0 °C due to oxide dissolution but no pitting. The Nd:YAG laser weld in 1mm material, but in both cases a switch to
figure shows that in the majority of cases the weld CPT was close hybrid welding with leading GTA or GMA gave a significant
to that of the base material. This even applies to autogenous improvement.
welds, where there is no filler metal added to adjust the weld

GTA-2.5 mm (A) (A)


GTA-2.5 mm (B) Base material
GTA-2.5 mm (C) Weld
GTA-5 mm (A) Weld with nitrogen
GTA-5 mm (B)

Top
GTA-5 mm (C)
Nd:YAG-1 mm (A)
Nd:YAG-1 mm (B)
Nd:YAG/GTA-1 mm (B)

CO2-1 mm (A)
CO2-2 mm (A) (B)
Fiber-1 mm (A)
Fiber/GMA-1 mm (C)
Root

Fiber-2 mm (A)
Fiber/GMA-2 mm (C)
Nd:YAG-1 mm (A)
Nd:YAG-1 mm (B)
Nd:YAG/GTA-1 mm (B)

0 10 20 30 40 50
CPT (°C)

Figure 8 Critical pitting temperatures for various welds in the lean duplex grade S32101, based on data from [6,7]. These include GTA and Nd:YAG, CO2 or fiber laser
welds which were either autogenous (A) or with a filler (B = W 23 7 N L, C = W 22 9 3 NL or G 22 9 3 NL). Micrographs show a reduction in the amount of surface
nitride for GTA welds with Ar + 2% N2 (lower photograph) compared to pure argon (top) but little difference in CPT. The lower CPT values (circled) were improved by
hybrid welding.
1/2014 | 7

Conclusions References
Results presented in this paper have demonstrated that excellent [1] H. Liu, P. Johansson and M. Liljas: Structural evolution of LDX
pitting corrosion resistance, on a par with that of the base material, 2101 (EN1.4162) during isothermal ageing at 600 – 850 °C.
can be achieved for welds in duplex stainless steels. A critical Proc. 6th European Stainless Steel conference, Helsinki
factor is the removal of weld oxide by pickling, or minimization of 2008).
oxidation by efficient use of shielding and backing gas. Nitrogen [2] E. M. Westin: Pitting corrosion resistance of GTA welded lean
additions to the shielding gas can also have a beneficial effect on duplex stainless steel. Welding in the World 54 (2010) 11/12
weld metal pitting resistance by increasing the weld metal nitrogen R308-321.
content and promoting austenite reformation. The high nitrogen
[3] E. M. Westin & D. Serrander: Experience in welding stainless
content of the lean duplex steel UNS S32101 means that good
steels for water heater applications. Welding in the World I56
corrosion resistance can be achieved even in autogenous GTA
(2012) 5/6 14 – 28. IIW Doc.-No. IX-2357-11
welds, laser welds and resistance spot welds.
[4] E. M. Westin, M. M. Johansson and R. F. A. Pettersson: Effect
of nitrogen-containing shielding and backing gas on the pitting
corrosion resistance of welded lean duplex stainless steel
EN 1.4162. IIW Doc. II-C-437-11. Accepted for publication in
Welding in the World.
[5] A. Thulin, M. Johansson, S. Mameng: Properties of resistance
spot welded duplex stainless steel. Proc. Duplex Stainless
Steel World 2010
[6] E. M. Westin: Corrosion resistance of welded lean duplex
stainless steel. Proc. Stainless Steel World 2008.
[7] M. M. Johansson, E. M. Westin, J. Oliver and R.F.A. Pettersson:
Localised corrosion resistance of welded austenitic and lean
duplex stainless steels. Welding in the World 55 (2011) 9/10
19 – 27.

Reproduced with permission from NACE International, Houston, TX.


All rights reserved. Paper C2013-002697 presented at CORROSION/2013, Orlando, FL.
© NACE International 2013.
1357.EN-GB, Art 58, 04, 14.
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