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A CORROSION MANAGEMENT AND APPLICATIONS ENGINEERING MAGAZINE FROM OUTOKUMPU

Qualification Testing of
Lean Duplex Stainless Steels
for the Process Industry

3/2014

3/2014 |

Qualification Testing of
Lean Duplex Stainless Steels
for the Process Industry
Rachel Pettersson, Carolina Canderyd, Jan Y. Jonsson,
Avesta Research Centre, Outokumpu Stainless AB, Avesta, Sweden,
Poul-Erik Arnvig, Outokumpu Stainless North America, Schaumberg, IL, USA.

Abstract

Introduction

The materials specifier needs accepted methods for qualification


or assurance testing to verify that supplied materials have
acceptable properties. For duplex stainless steels the ASTM A923
standard has found extensive use as a qualification test for the
duplex UNS S32205 and superduplex S32750 grades, where the
primary cause for concern is the precipitation of intermetallic
phases. However, lean duplex grades such as UNS S32101 or
UNS S32304 present more of a challenge because these steels
are much less sensitive to intermetallic phase precipitation than
the higher alloyed duplex grades. The small microstructural
changes associated with improper heat treatment are challenging
to detect and impact toughness acceptance limits need definition.
The ferric chloride immersion test used in ASTM A923 results in
sub-ambient temperatures for lean duplex grades and is therefore
in many instances impractical to use.
The approach explored in the present work is the use of an
inhibited 5% ferric chloride solution containing additions of 1%
sodium nitrate. This leads to critical temperatures for the onset of
pitting which are around or above ambient. Results are presented
showing the influence of the level of nitrate additions on the
corrosion performance and also correlated to impact toughness
data. Application to various product forms is discussed, together
with proposed acceptance criteria. Finally, a limited laboratory
intercomparison of the test method is presented.
These results represent steps towards development of a new
variant of ASTM A923 for lean duplex stainless steels, which is
aimed to remove any remaining uncertainty when specifying such
grades.

Qualification or acceptance testing is often required by the


materials purchaser in order to be able to verify that delivered
material is in an acceptable condition and will fulfill the property
requirements placed on the grade. The ASTM (1) A923 standard is
an established test for the standard duplex grade UNS S32205
and the superduplex S32750. Both these grades are sensitive to
the precipitation of intermetallic phases, typically in temperature
range 800 1000C, Figure 1.
The ASTM A923 test describes three methods. Method A
involves electrolytic etching in sodium hydroxide solution to reveal
microstructural changes. Intermetallic phases such as sigma
phase are usually seen as discrete particles at grain and phase
boundaries and can easily be detected using the required
magnification of 400 500x. According to the standard this type
of screening test can be used to pass material which has an
acceptable, unaffected structure, but if the microstructure appears
affected or possibly affected this must be followed up by testing
according methods B or C. Method B involves Charpy-V impact
testing at -40C (-40F) while Method C involves immersion testing
in 6% ferric chloride solution, with the requirement that the weight
loss at the specified temperatures should not exceed 10 mdd
(mg/dm2/day) measured in a 24 hour test. In practice, these two
readily quantifiable tests are often used in preference to the
metallographic screening.

11000
S32750
1000

Key words: stainless, testing, corrosion, sensitization, lean duplex,


qualification, acceptance
Temperature (C)

900
S32205
800

S32101

S32304

700
600
500
400
300
0.01
(36 s)

(1)
ASTM International, 100 Barr Harbor Drive, PO Box C700, West
Conshohocken, PA, 19428-2959, USA.

0.1
(6 min)

1
Time (h)

10

Figure 1 TTT diagram shown here as the times to obtain 50% reduction
in impact toughness. [2]

100

3/2014 |

The lean duplex grades such as UNS S32101 and UNS


S32304 show a very different type of behavior if they are subject
to inappropriate heat treatments. Most rapid precipitation of
secondary phases occurs at lower temperatures, typically
600 1800C, as seen in Figure 1. This is primarily associated
with the precipitation of chromium nitrides and carbides. [2]
Intermetallic phases appear first after much longer ageing times,
typically in excess of 10 hours at the most sensitive temperature,
and are thus very unlikely to be an issue.
The methodology described in ASTM A923 is unfortunately
difficult to apply to lean duplex grades for a number of reasons.
Firstly, the sodium hydroxide etching in Method A is not suitable for
revealing the fine phase boundary precipitates which are involved,
even though this can be done by an experienced microscopist
working at fairly high magnification. The impact toughness in
Method B is not particularly sensitive for lean duplex grades at

-40C [3] while the ferric chloride testing in Method C results in


sub-ambient temperatures which are impractical to work with in
many laboratories.
The approach addressed in this work is the use of an inhibited
ferric chloride solution containing additions of sodium nitrate. The
sodium nitrate acts as an inhibitor, and increases the critical
temperatures for the onset of pitting to around or above ambient,
thus providing the possibility for a simple and practical acceptance
test. This concept has been addressed in a number of recent
works on lean duplex grades, [3, 4, 5] and was also discussed
many years ago within the ASTM G48 working groups, for lower
alloyed austenitic grades.[6] The aim of the present work is to
apply the inhibited ferric chloride test to a range of product forms
in the two lean duplex grades UNS S32101 and UNS S32304
order to examine its validity and usefulness.

Materials and Experimental Procedures


Materials
The investigated materials were UNS S32101 (EN 1.4162,
Outokumpu LDX 2101(2)) and UNS S32304 (EN 1.4362,
Outokumpu 2304(2)), with the typical compositions given in Table 1.
Various product forms were investigated as specified in Table 2.
These were investigated in the mill annealed condition, and also after
a number of laboratory heat treatments designed to simulate the
variation in annealing conditions which are likely to be encountered
in different mills. In addition, sensitizing heat treatments were
performed at 700C, which is the temperature of most rapid
precipitation of secondary phases according to Figure 1. The
sensitizing times ranged from 1 minute to 30 hours and are the
holding times at the respective temperature, as detailed in
previous work. [3]

Steel grade and dimension (mm)

Product

UNS S32101

UNS S32304

Plate

12, 30

20, 30

Sheet

0.51.5

1.56

Tube

27x2

27x1.5

Rebar/bar

1625

Table 2 Tested products from the two grades.

UNS

EN

Cr

Ni

Mo

Mn

S32101

1.4162

0.03

0.22

21.5

1.5

0.3

S32304

1.4362

0.02

0.10

23

4.8

0.3

1.5

Table 1 Nominal compositions of the grades investigated.

Inhibited Ferric Chloride Tests


An inhibited test solution comprising 5 wt% FeCl3 + 1 wt% NaNO3
was used as described previously. [3, 5] Samples were cut to
approximate dimensions of 50 x 25 mm. All surfaces were dry
ground to a 120 grit finish as used in ASTM A923, followed by an
acetone rinse. The exceptions were some tube, rebar and welded
samples which were pickled, rather than being ground, in order to
retain the original surface which is typical for the products in
question. According to ASTM A923 testing of a specimen in the
as-fabricated condition, rather than undergoing the prescribed
grinding to 120 grit, is permitted if this is relevant to the application. All samples were weighed to the nearest 0.0001 g and the
dimensions measured. The majority of testing was performed at
the Avesta Research Centre laboratories (denoted Lab A); while
Lab D and Lab N participated in the inter-laboratory comparison.
Testing was performed in glass beakers with a minimum of

(2)

Trade name.

600 ml of test solution (150 ml at Lab N). The test temperature


was controlled to 1C. Each test involved immersion for 24 hours,
after which the exposed samples were cleaned, rinsed and dried.
Samples were then re-weighed and the corrosion rate calculated
in units of mg/dm2/day (mdd). Each condition was tested at various
temperatures to determine the pitting temperature as a function
of the ageing time. A corrosion rate greater than 10 mdd was used
as a threshold for unacceptable performance, which is the same
acceptance criterion used in the ASTM A923 Method C. The critical
temperature was defined as the highest temperature at which the
corrosion rate was below this limit.
In order to assess the electrochemical behavior of lean duplex
grades in nitrate-inhibited chloride solutions, polarization curves
were also obtained at a scan rate of 20 mV/minute in 5.5 wt.%
NaCl solutions which were acidified to pH 1.3 and modified by
various additions of NaNO3.

3/2014 |

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RESULTS
Electrochemical tests in nitrate inhibited solutions

1.E +04
45C,
5.5% NaCl
1.5% NaNO3

Current density (A/cm2)

1.E +03

1.E +02

8C,
5.5 NaCl

1.E +01

1.E +00

1.E -01
-1000

-500

0
Potential (mVSCE)

500

1000

1200
1.1% NaCl
0.3% NaNO3

Breakdown potential (mVSCE)

1000

5.5% NaCl
2% NaNO3

5.5% NaCl
800

Immersion testing in inhibited ferric chloride

5.5% NaCl
0.5% NaNO3

600

400

200
0

80

10

20

30
40
50
Temperature (C)

60

70

80

1.1% NaCl

Critical pitting temperature (C)

70
60
3.3% NaCl

50
40

5.5% NaCl

30
20
10
0

0.0

0.2

Polarization curves in acidified sodium chloride with and without


additions of sodium nitrate are shown in Figure 2 and demonstrate
the presence of a slight tendency to an active corrosion peak at
~-350mVSCE, which is depressed by nitrate additions. There is also
an earlier onset of transpassive corrosion, at ~900 mVSCE in the
presence of nitrate. If the breakdown potentials (defined as the
potential at which the anodic current density exceeds 100 A/cm2)
are plotted as a function of temperature it is seen that there is a
sharp transition between the transpassive behavior at lower
temperatures and the pitting behavior, typically at potentials of
<300 mVSCE, at higher temperatures. This transition is denoted the
critical pitting temperature (CPT) and plotted as a function of the
NO3-/Cl- in the third diagram in Figure 2. The CPT shows a virtually
linear increase as the level of nitrate is increased in the range
0.5 2%. Use of a more dilute solution of 1.1% NaCl + 0.3% NaNO3
(i.e. with concentrations which were employed in [4] gives somewhat
higher CPT, as is to be expected.
The open circuit potential measured in the inhibited ferric
chloride test (5 wt% FeCl + 1 wt% NaNO) is close to 700 mVSCE,
and it is seen from Figure 2 that this potential lies in the middle of
the transition region and is thus well within the region in which the
critical pitting temperatures is largely potential-independent [7].

0.4

0.6

NO3 /Cl ratio


Figure 2 Use of polarization curves in acidified NaCl + NaNO3 to evaluate critical
temperatures for the transition between transpassive corrosion and pitting for
3 mm sheet of UNS S32101.

In Figure 3 the results of inhibited ferric chloride tests on a range


of products of UNS S32101 and UNS S32304 are shown. The
solid points represent temperatures at which the weight loss is
>10 mdd, thus corresponding to a fail if the same acceptance
criteria are applied as in ASTM A923. The open points represent a
pass. The normal procedure used here is to test two specimens,
but for clarity only a single point is given at each temperature and
a pass given only if both specimens have a weight loss of 10
mdd or below.
For UNS S32101 the thicker (30 mm) plate materials all pass
the test at 30C, although there are some cases in which the
critical temperature may be higher. The 1.5 mm sheet material has
an even more homogenous structure as a result of cold rolling and
this give a slightly higher critical temperature of >40C. After a
holding time of 5 minutes at 700C a drop in the critical temperature is discerned, with slightly more rapid sensitization being seen
for the thinner 1.5 mm sheet material.
The trends for UNS S32304 were somewhat less pronounced.
The annealed states showed critical temperature ranging from
45C for the 30 mm plate to 30C for the 20 mm plate and
1.5 mm sheet. There was little effect of shorter sensitization
times, but a clear drop was seen after >1 hour at 700C. This is in
agreement with data reported in the literature that for a significant
level of sensitization of the UNS S32304 grade, sensitization times
longer than 10 hours are usually needed.[8] In contrast to UNS
S32101, the investigated sheet material showed slightly more
rapid sensitization than the 30 mm plate, while the 20 mm plate
showed very little effect.
The challenge in trying to define an acceptance criterion for
a qualification test is that all product forms must pass the test
when in a correct mill-finished condition but at the same time fail
if the material has been sensitized to a detrimental extent. The
annealing temperature and cooling rate affect the phase ratio
and also the partitioning of alloying elements between the phases,
thus the corrosion resistance. In addition thick plate has a much
coarser structure than cold rolled sheet and may show a great

3/2014 |

degree of segregation, while bar material, and particularly rebar,


may have undergone a process annealing step rather than a
separate solution annealing stage. Corrosion results from all the
product forms tested for UNS S32101 and UNS S32304 are
shown in Figure 4 and indicate that for both grades an acceptance
temperature of 20 or 25C fills the specified requirements.
For UNS S32101, the data presented in previous work indicated
that good welds in 12 30 mm plate show a pass temperature in

60
50

122F

40

104F

30
86F

20
68F

10

70

168F

Annealed

S32304, 30 mm

40
30
20

70
mdd<10
mdd>10

50

122F

40

104F

30
86F

20
68F

10

Annealed

Annealed

0.1
1.0
10.0 100.0
Time at 700C/1292F (hours)

40
30
20

Annealed

70

S32304, 12 mm

mdd<10
mdd>10

50
40
30
20

mdd<10
mdd>10

50

0.1
1.0
10.0 100.0
Time at 700C/1292F (hours)

10

50F

S32101, 1.5 mm

60

10

60
Test temperature (C)

140F

Test temperature (C)

50

0.1
1.0
10.0 100.0
Time at 700C/1292F (hours)

60

mdd<10
mdd>10

10

50F

70

S32101, 12 mm

60
Test temperature (C)

Test temperature (C)

140F

70
mdd<10
mdd>10

Test temperature (C)

S32101, 30 mm

0.1
1.0
10.0 100.0
Time at 700C/1292F (hours)

S32304, 1.5 mm

mdd<10
mdd>10

60
Test temperature (C)

70

168F

the range 35 45C and can thus be treated in the same way as
the base material. [3] For UNS S32304 even longer sensitization
temperatures than 10 hours are really needed to see a clear
degradation in corrosion properties, but it can be argued that this
is hardly realistically likely to be encountered so this material can
be regarded as fairly resistant to structural degradation caused by
inappropriate heat treatment.

50
40
30
20
10

Annealed

0.1
1.0
10.0 100.0
Time at 700C/1292F (hours)

Annealed

0.1
1.0
10.0 100.0
Time at 700C/1292F (hours)

Figure 3 Results of inhibited ferric chloride corrosion testing for different product forms of UNS S32101 (upper three diagrams) and UNS S32304 (lower three).
Each set of vertical points to the left hand side of the diagrams represents a different variant of annealing.

70

S32101

30 mm plate
12 mm plate
1.5 mm sheet
27x2 mm tube
Bar/rebar

60

140F

Test temoerature (C)

50

122F

S32304
30 mm plate
20 mm plate
6 mm plate
1.5 mm sheet

60
50
Test temoerature (C)

70

168F

40

104F

30

86F

20
68F

10

40
30
20
10

50F

0
Annealed

0.1

1.0

10.0

Time at 700C/1292F (hours)

100.0

0
Annealed

0.1

1.0

10.0

Time at 700C/1292F (hours)

Figure 4 Compilation of corrosion data for various product forms of UNS S32101 and UNS S32304. For annealed states the critical temperatures
are arranged in descending order for clarity. An acceptance limit of 20 25C appears appropriate.

100.0

3/2014 |

Effect of test variables

observed. If the specimens were instead thoroughly cleaned, using


sand blasting followed by laboratory pickling, failure was seen only
at 55C or higher.
Tube material was tested both in the as-fabricated condition, as
is permitted in ASTM A923, and after dry surface grinding to 120
mesh finish, which is required for mill products. The effect was
minor to negligible, with failure in both cases occurring at 55C.
Likewise use of a newly-prepared test solution, or one which had
been made up from a stock test solution prepared a week before,
had only minor impact when applied to 12 mm UNS S32101.
Cleaning specimens with acetone or a magnesium oxide paste had
no significant effect on the weight loss when tested above the
critical temperature
Finally, two different test solutions were compared: the
5% FeCl3 + 1% NaNO3 which forms the basis of this work, and the
1% FeCl3 + 0.3% NaNO3 which has been investigated in other work.
[4] It can be recalled from Figure 2 that a more dilute NaCl+NaNO3
solution gave rise to a electrochemically evaluated critical pitting
temperature which was some 10C higher. However, the immersion
testing actually yielded the same critical temperatures. This may
reflect the lower degree of precision typically associated with
immersion testing, but merits more extensive investigation.

Any acceptance test needs to be examined in order to evaluate


whether test variables have such significance that they need to be
tightly controlled or whether a certain amount of variation can be
permitted. Figure 5 shows the application of such sensitivity
analysis to various variants of UNS S32101. Two effects appear
very clearly: the starting temperature and the presence of weld
oxides. If the specimen is placed directly into the preheated test
solution, as is specified for the ferric chloride testing of duplex and
superduplex grades in ASTM A923, then the critical temperature is
lower than if the specimen is placed in a room temperature
solution and then heated up to the test temperature. In the case
shown, the latter leads to a pass at 60C, while failures are seen
at 35C for the correct procedure.
Allowing oxides, from annealing or welding, to remain on the
specimen surface also had a critical influence. The presence of
weld oxides caused failures due to the weight loss exceeding
10mdd for 6 mm UNS S32101, at temperatures as low as 20C.
However, there were no pits seen on these specimens, so it is
apparent that the measured weight loss is related to the dissolution of the weld oxides in the ferric chloride solution rather than to
actual corrosion attack. Not until 45C was pitting attack

70

70

S32101, 30 mm

30
20
mdd<10 pass
mdd>10 fail

10
0

70

Start at
test temp.

30

mdd 6.212.0

20

Start
at RT

mdd<10 pass
mdd>10 fail
Pits
0

70

S32101, 12 mm

50
40
30
20
mdd<10 pass
mdd>10 fail

10
0

Start at
test temp.

Start
at RT

As
welded

S32101, 12 mm

60
Test temperature (C)

Test temperature (C)

40

10

60

50

50

50
40
30
20
mdd<10 pass
mdd>10 fail

10
0

Sand blast
+ pickled

70
mdd

10682

8986

3438

3768

40
30
20
10
0

Test temperature (C)

40

S32101, 27x2 mm tube

60

As rec.

S32101, 12 mm

50
40
30
20
mdd<10 pass
mdd>10 fail

10
0

Acetone

MgO

120#

60
Test temperature (C)

50

70

S32101, 6 mm

60
Test temperature (C)

Test temperature (C)

60

Figure 5 Effect of test variables on results from the inhibited ferric chloride test. Each marked point represents a single sample.

5% FeCl3
+1% NaNO3

1% FeCl3
+0.3% NaNO3

3/2014 |

Inter-laboratory comparison

material and this was the subject of intense investigation, as


witnessed by the large number of test points in the diagram.
At Lab A the material passed at 40C but showed some failures
at 45C, while at Lab N there were passes up to 60C with only
a single failure among sixteen tests conducted at 50C. Lab D
showed results intermediate between these two extremes. An
exhaustive search of reasons behind this difference yielded only
one tentative explanation: that it could be related to the presence
of some remaining surface oxide or underlying depletion. As seen
in Figure 5 oxides can have a large effect on the evaluated critical
temperature, and it was found that Lab N removed much more
material by grinding than did Lab A. There is thus a risk that there
may be some surface effects remaining in the Lab A tests.

A second aspect necessary to establish the robustness of a test


method is to verify that the same, or sufficiently similar, results can
be achieved at different laboratories. Three UNS S32101 materials
were selected for a small Round Robin: 12 mm plate which had
been laboratory annealed, a variant which had been sensitized
for 5 minutes at 700C and 27x2 mm tube material with both an
as-received and 120 mesh ground surface. The results in Figure 6
show excellent agreement in the two latter cases even though
there were some differences in test procedure. For example Lab A
used the prescribed solution volume of 600 mL while Lab N used
a smaller amount of 150 mL.
The only discrepancy observed was for the laboratory annealed

mdd<10 pass
mdd>10 fail

50
40
30
20

70

S32101, 12 mm. Sense 700C/5 min

60
50
40
30
20

50
40
30
20

10

10

10

Lab A

Lab D

Lab N

S32101, 27x2 mm tube

60
Test temperature (C)

60
Test temperature (C)

70

S32101, 12 mm. Lab annealed

Test temperature (C)

70

Lab A

Lab N

As-received
Lab A

Lab N

120# ground
Lab A

Lab N

Figure 6 Results of inter-laboratory comparisons show some difference for solution annealed material (left) but good agreement for sensitized material and tube.

Comparison with other corrosion testing methods

the grade. [11] After sensitization for 5 minutes at 700C pitting


occurs at 0C. A comparison with results from electrochemical
testing in 1M NaCl according to ASTM G150 [10] is also included
in Table 3 and shows the same trend of a clear drop as the result
of sensitization. The data for UNS S32304 indicates that the
electrochemical testing even seems to be more sensitive to
inappropriate heat treatment than immersion testing. However,
this type of testing is impractical for qualification and acceptance
purposes since the necessary equipment and electrochemical
know-how are not so extensively available.

As mentioned in the Introduction the use of ASTM A923 Method C


for lean duplex grades results in impractically low testing temperatures, or at least the requirement of cooling baths which are not
standard in many laboratories. The same applies to immersion
testing in ferric chloride solution according to ASTM G48. [9]
However, a limited comparison with the latter is included in Table 3
in order to put the present results into perspective. It is seen that
the critical temperature according to ASTM G48E is 5 10C,
which is actually on the low side compared to normal values for

Grade

5% FeCl3 + 1% NaNO3
Max pass temp.
(mdd < 10)

6% FeCl3+1% HCl
ASTM G48 E

1M NaCl
ASTM G150

15C

1520C

40C

5C (visible pit)
10C (mdd>10)

15.4C

25C

0C

9.6C

20 25C

Annealed

30C

27C

1 h, 700C

25C

6C

10 h, 700C

25C

2.8C

Condition
Normal values

UNS S32101
(12 mm)

Lab annealed
5 min 700C
Normal values 11

UNS S32304
(20 mm)

Table 3 Comparison between different corrosion test methods.

3/2014 |

An extensive evaluation of the metallography of sensitization in the


lean duplex grades UNS S32101 and UNS S32304 has been
presented recently.[3] The 40% sodium hydroxide (NaOH) etchant
specified in ASTM A923 was used, with an applied voltage of 2 V
for 10 seconds (the specification in the standard is 1 3V for
5 60 seconds) and it was found that this did give some indication
of detrimental phase boundary precipitates, but that such
identification was challenging, as seen in Figure 7. An alternative
method of electrolytic etching in 10% oxalic acid (C2H2O4) at room
temperature and 6 7 V for 10 seconds was found to be much
more revealing of the fine carbides in the phase boundaries and
nitrides within the ferrite phase, and to give a good first indication
of sensitization. This etchant is therefore recommended as a
preferable equivalent to ASTM A923 Method A for lean duplex
grades. It should, however, be pointed out that this metallographic
evaluation can be more of a challenge for thinner gauge materials
and that very low but non-detrimental levels of precipitates are
also often present in mill annealed material.
The use of impact toughness as a qualification or acceptance
test for lean duplex grades was also investigated in and it was
concluded that a good sensitivity could be achieved by using a test
temperature of 20C for UNS S32101 and 20C or perhaps even
better -10C for UNS S32304. [3] Two examples are shown in

Figure 8 and indicate that a clear distinction between annealed


and sensitized material can be detected. The impact toughness for
12 mm plate material of UNS S32101 has decreased from ~180J
in the solution annealed condition to 50 60J after 5 minutes at
700C. This degradation is also seen in the corrosion properties
and in the oxalic acid etched microstructure. The corresponding
curve for 30 mm plate of UNS S32304 indicates that the impact
toughness drops after 0.5 to 1h to a level around 150J at room
temperature or 100J at -10C. However, the real drop in toughness
for this grade is not really seen until sigma phase begins to
precipitate at <10 hours, as indicated in Figure 1. Testing at -10C
appears to be slightly more sensitive to microstructural impairment
for UNS S32304 but this slight advantage has to be weighed
against the disadvantages of multiple testing temperatures and
need for cooling specimens.
Both corrosion and impact toughness testing seem to give
similar results, in terms of the time at 700C before a drop in
properties is seen, although impact toughness may be marginally
more sensitive. Both tests should nevertheless be interchangeable
to use for approving or rejecting a lean duplex batch of material.
A requirement should be placed on the number of specimens to
be tested, and it would be appropriate to require a single pass,
or a pass of both retested specimens in case of a first failure, as
is specified in ASTM A923 today for standard and superduplex
stainless steels.

70

S32101, 12 mm
CV (J)
mdd<10

60

Test temoerature (C)

50

200

150

40
100

30
20

50

Charpy impact toughness (J)

Comparison to metallographic evaluation


and impact toughness

10
0

(a) 40% sodium hydroxide. 2V, 10 seconds

0.1

Annealed

1.0

0
100.0

Time at 700C/1292F (hours)


350

S32304, 30 mm
CV (RT)
mdd<10
CV (-10C)

60

Test temoerature (C)

50

300
250

40

200

30

150

20

100

10

50

0
Annealed

0.1

1.0

10.0

Charpy impact toughness (J)

70

(b) 10% oxalic acid. 6 7V, 10 seconds

10.0

0
100.0

Time at 700C/1292F (hours)


Figure 7 Microstructure of UNS S32101, 12 mm plate, sensitized for 5 minutes
at 700C showing the advantages of electrolytic etching in oxalic acid over
sodium hydroxide

Figure 8 Corrosion resistance and impact toughness for tested 12 mm plate


of UNS S32101 and 30 mm plate of UNS S32304 showing how the impact
toughness drop occurs marginally before the effect on corrosion resistance.

3/2014 |

Future prospects
The ASTM subcommittee A01-14 has recently established a
working group to look into the question of standardization of
acceptance testing for lean duplex grades. [12] This group will
establish a proposal for a formal standardization of the test
methods as well as guidelines for acceptance criteria for different
alloys and products. The indications from the present work are that
the lean duplex UNS S32101and UNS S32304 in the dimensions
and products investigated here could be expected to pass an
inhibited ferric chloride corrosion test at 20 25C if correctly heat
treated. The impact toughness values attainable seem to surpass
the minimum values in the transverse direction specified in the
materials standard EN 10088-2/4 of 40J for UNS S32101 and

Grade/condition

ASTM A923

Lean duplex
(this work and [3])

60J for UNS S32304. Thus it may be appropriate to specify


somewhat higher limits based on the present data. Suggestions
for limits and a comparison with the current acceptance criteria for
duplex and superduplex grades according to ASTM A923 are given
in Table 4. From the data presented here it seems that UNS
S32101 reasonably attains 60 80J at room temperature, while
the corresponding value for UNS S32304 may be in excess of
100J However, there are indications that -10C might be a more
sensitive impact test temperature for this steel. [3] Whatever
criteria are set, the guiding principle must be that the proposed
limits should be sensitive to different degrees of sensitization and
be capable of clearly distinguishing materials with detrimental
levels of carbides and nitrides from properly annealed states.

A:
Etching

B:
Requirements impact

C:
Requirements corrosion

UNS S32205
base material

40% NaOH
electrolytic

54J -40C
(40ft-lb -40F)

6% FeCl3,<10 mdd
25C (77F)

UNS S32205
weld metal

40% NaOH
electrolytic

34J -40C
(25 ft-lb, -40F)

6% FeCl3<10 mdd
22C (72F)

UNS S32750
base material

40% NaOH
electrolytic

To be agreed

6% FeCl3<10 mdd
40C (104F)

Grade/condition

Proposal etching

Proposal impact

Proposal corrosion

UNS S32101
base material

10% C2H2O4

6080J, RT

5% FeCl3 + 1% NaNO3
< 10 mdd, 20 25C

UNS S32304
base material

10% C2H2O4

100J, RT
or 6080J, -10C

5% FeCl3 + 1% NaNO3
< 10 mdd, 20 25C

Table 4 Acceptance criteria for UNS S32205 and UNS S32750 from ASTM A923 and comparison with proposed criteria for lean duplex grades
UNS S32101 and UNS S32304 from this work.

3/2014 |

10

Conclusions

References

There are good possibilities to be able to define a qualification or


acceptance test for the lean duplex grades UNS S32101 and UNS
S32304 which parallel the methods specified in ASTM A923 for
the higher alloyed duplex steels UNS S32205 and S32507.
Immersion testing with weight loss evaluation in a 5% ferric
chloride solution inhibited by the addition of 1% sodium nitrate is
suitable for differentiation between acceptable solution annealed
states and unacceptable detrimental sensitizing heat treatments.
The proposed acceptance test temperature is 20 or 25C. This
has the advantage of avoiding the need for cooling baths for the
sub-ambient temperatures which would be required in uninhibited
ferric chloride.
The test method has shown good inter-laboratory comparability
and robustness in terms of surface grinding, cleaning and the way
in which the solution is prepared. However, it is sensitive to the
presence of residual weld oxides. It is also important that the
specimen be placed in the preheated test solution to avoid false
passing results which arise if the specimen is heated from ambient
in the solution.
There is good correlation with between loss of corrosion
resistance and a drop in impact toughness. A screening evaluation
based on electrolytic etching in 10% oxalic acid can be obtained
to give a good first indication of a substandard material before
proceeding to corrosion or impact toughness testing. Definition
of acceptance limits requires further work, preferably under the
auspices of the working committee established under ASTM A01.14.

[1] ASTM A923-08 Standard Test Methods for Detecting


Detrimental Intermetallic Phase in Duplex Austenitic/Ferritic
Stainless Steels.

Acknowledgements
Anette Wallin, ARC, Outokumpu Stainless AB is gratefully acknowledged
for carrying out the immersion tests in FeCl3+NaNO3 and Sukanya
Mameng for the electrochemical work. Thanks are also expressed
to James D. Fritz, TMR, for valuable discussions and to laboratories
N and D for participating in Round Robin testing.

[2] H Liu, P Johansson and M. Liljas: Structural evolution


of LDX2101 (EN 1.4162) during isothermal ageing at
600-850C. Proc. 6th European Stainless Steel Conference,
Helsinki (2008), p555-560
[3] J. Y. Jonsson, C. Canderyd, R. Pettersson: Optimisation of a
qualification test method for lean duplex stainless steels.
Paper 28 presented at 7th European Stainless Steel Science
and Market conference, September 2011, Como, Italy
[4] P. Boillot, R. Bergeron, J. Peultier, K. Wiegers and T. Ladwein:
Investigations on standard corrosion test for quality control of
lean duplex stainless steel. Proc. 8th Duplex Stainless Steels
conference, Beaune (2010), Beaune.
[5] J. D. Fritz, P-E. Arnvig, J. Y. Jonsson, R. Pettersson and
S. Randstrm: Evaluation of possible test methods for
qualifying lean duplex stainless steel Proc. Stainless Steel
World, Houston, Texas (2010).
[6] Arne Bergqvist, personal communication
[7] R. Qvarfort: The Avesta cell a new tool for studying pitting.
ACOM 1988 vol 23 p 25
[8] M. Liljas, P Johansson, H-P Liu, C-O Olsson: Development of
a lean duplex stainless steel. Steel Research International.
Vol. 79, no. 6, pp. 466473. June 2008
[9] ASTM G48-11 Standard Test Methods for Pitting and Crevice
Corrosion Resistance of Stainless Steels and Related Alloys
by Use of Ferric Chloride Solution
[10] ASTM G150 -99 (2010) Standard Test Method for
Electrochemical Critical Pitting Temperature Testing
of Stainless Steel
[11] Outokumpu Corrosion Handbook, 10th Edition, 2009,
Outokumpu Oyj, Espoo, Finland
[12] www.astm.org

Reproduced with permission from NACE International, Houston, TX.


All rights reserved. Paper No. C2012-0001527 presented at CORROSION/2012, Salt Lake City, UT.
NACE International 2014.

1548.EN-GB, Art 58, 10, 14.

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