Accepted Manuscript

Title: Thermal aging at 475 ◦ C of newly developed lean duplex

stainless steel 2404: mechanical properties and corrosion
behavior

Author: <ce:author id="aut0005"

author-id="S0010938X16310824-
0b538877ee824d03bfd522c51c4a2883"> R. Silva<ce:author
id="aut0010" author-id="S0010938X16310824-
36f0b81aaf9650963f37684bb4866464"> L.F.S.
Baroni<ce:author id="aut0015"
author-id="S0010938X16310824-
a67e0dded9bfe8f33b78b6b63ffa24c5"> C.L.
Kugelmeier<ce:author id="aut0020"
author-id="S0010938X16310824-
be23a3b840ebabe3ee66811692f9c9dc"> M.B.R.
Silva<ce:author id="aut0025"
author-id="S0010938X16310824-
e9fb9698df58bc422ebddd36355a287f"> S.E. Kuri<ce:author
id="aut0030" author-id="S0010938X16310824-
9df1d1637400d63ad0e6e0b53c787858"> C.A.D.
Rovere

PII: S0010-938X(16)31082-4
DOI: http://dx.doi.org/doi:10.1016/j.corsci.2016.12.014
Reference: CS 6963

To appear in:

Received date: 31-10-2016

Revised date: 24-12-2016
Accepted date: 30-12-2016

Please cite this article as: R.Silva, L.F.S.Baroni, C.L.Kugelmeier, M.B.R.Silva,

S.E.Kuri, C.A.D.Rovere, Thermal aging at 475◦ C of newly developed lean duplex
stainless steel 2404: mechanical properties and corrosion behavior, Corrosion Science
http://dx.doi.org/10.1016/j.corsci.2016.12.014
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 1

Thermal aging at 475 °C of newly developed lean duplex stainless

steel 2404: mechanical properties and corrosion behavior

R. Silva(a), L.F.S. Baroni(a), C.L. Kugelmeier(a), M.B.R. Silva(b), S.E. Kuri(a),

C.A.D. Rovere*(a)
a
Munir Rachid Corrosion Laboratory, Department of Materials Engineering, Federal
University of São Carlos, Rodovia Washington Luis Km 235, 13565-905 São Carlos,
SP, Brazil
b
Structural Characterization Laboratory, Department of Materials Engineering, Federal
University of São Carlos, Rodovia Washington Luis Km 235, 13565-905 São Carlos,
SP, Brazil

* Phone: +55 16 33518507; Fax: +55 16 33518258

Email addresses: [email protected]; [email protected]

 2

Highlights

 Influence of thermal aging at 475 °C on LDSS 2404 has been assessed.

 The presence of α′ phase decreases ferromagnetic behavior of the
LDSS.
 An increase in hardness and drastic loss in absorbed energy of the
LDSS was detected.
 The α' phase formation occurs by spinodal decomposition.
 The degradation of corrosion resistance is slower in LDSS 2404 than in
DSS 2205.

ABSTRACT

An investigation was made of the effect of aging for up to 2000 h at 475 °C on

the properties of the newly developed lean duplex stainless steel (LDSS) 2404.
Due to its lower alloying content, the degradation of corrosion resistance as a
function of thermal aging evolves more slowly in LDSS 2404 than in a standard
duplex alloy (DSS 2205). The results also suggest that the mechanism of α'
phase formation in the ferritic matrix occurs by spinodal decomposition and that
this phenomenon has a stronger impact on the steel’s mechanical properties
than on its corrosion behavior.

Keywords: Lean duplex stainless steel; Thermal aging; Spinodal

decomposition; Microstructure; Corrosion; DL-EPR.

 3

1. Introduction

Duplex stainless steels (DSS) are engineering materials of great

technological importance because of their attractive combination of mechanical

properties and high corrosion resistance, which is the result of their dual-phase

structure composed of approximately equal volume fractions of ferrite and

austenite phases [1,2].

The first commercial grade DSS, which was developed by the German

steel manufacturer Krupp in the mid-1970s, was referred to as “DSS 2205.” The

success of this alloy steel encouraged manufacturers to produce other classes

of duplex containing larger or smaller amounts of alloying elements [3].

Currently, there are several classes of DSSs that are classified with respect to

their values of Pitting Resistance Equivalent Number (PREN), such as: lean

duplex; standard 2205; 25% Cr; super duplex; and hyper duplex [4,5].

More recently, lean duplex stainless steels (LDSSs) have attracted

considerable attention because of the high cost of adding alloying elements

(particularly Ni and Mo) [2,6–8]. LDSSs contain fewer alloying elements than

the standard DSS 2205 and are intended for applications in which they can

replace the 304 and even 316 austenitic grades. In this context, different types

of LDSS alloys are being increasingly produced; this is the case of the newly

developed LDSS 2404, which is predicted to present higher corrosion

resistance than the other types of lean duplex (i.e., LDSS 2101 and LDSS

2304) due to its higher Cr, Mo and N contents [9].

Previous studies have reported that the LDSS grade is more resistant to

thermal embrittlement because of its lower content of alloying elements than

 4

that of standard DSS grades [2,4,10]. At high temperatures, this phenomenon

can occur by precipitation of the σ phase (650 - 950 °C), and at temperatures

below 538 °C through the formation of α’ phase [2,11–15]. According to Zanotto

et al. [11], the embrittlement of these alloys at temperatures between 650 and

850°C is kinetically slow because of their low Mo content. A study carried out by

Tucker et al. [2], who compared aged DSS 2003 with the standard DSS 2205

aged between 260 and 482 ºC for up to 10000 h, also showed that the thermal

stability of LDSS 2003 was higher. The two aforementioned reports indicate that

minor alloying decreases the rate of embrittlement reactions in the ferrite phase

of DSS. However, Garfinkel and coworkers [16], who evaluated the impact

toughness of two LDSSs (LDSS 2101 and 2003) and one DSS 2205 aged at

427 °C for 1000 h, found that the impact toughness behavior of LDSS 2101 and

the standard 2205 after aging was similar, and attributed this contradiction to

the higher ferrite content present in the LDSS 2101. According to the authors,

as the formation of α’ phase takes place exclusively in the ferrite, it would be

expected that a material with a higher volume fraction of this phase would

present a more significant reduction in the impact toughness. On the other

hand, it should be mentioned that the difference observed by the authors in the

ferrite content (between the LDSS 2101 and DSS 2205) was very small (around

3%), suggesting that this fact plays only a minor role in the relatively poor

impact performance presented by the LDSS. These disparate findings suggest

that the hypothesis mentioned earlier does not always apply to the thermal

embrittlement of LDSSs, and that more studies are needed to better understand

the influence of the chemical composition/microstructure on the thermal

embrittlement of LDSS at low temperatures. In addition, very little information is

 5

available about the effect of thermal aging at low temperatures on the corrosion

resistance of LDSSs.

In view of the above and considering the paucity of studies on LDSS

aging at low temperatures, particularly of the newly developed LDSS 2404, the

aim of this study was to assess the effect of aging at 475 °C for up to 2000 h on

the corrosion and mechanical properties of a LDSS 2404. The microstructural

changes were analyzed by means of optical microscopy (OM), scanning

electron microscopy (SEM), transmission electron microscopy (TEM) and

ferritescope measurements. The mechanical properties were evaluated based

on Vickers microhardness measurements and Charpy impact tests. Double loop

electrochemical potentiokinetic reactivation (DL-EPR) tests were used to assess

the corrosion performance.

2. Experimental Procedure

2.1. Material

The material studied was LDSS 2404 supplied by Outokumpu Stainless

AB in the form of a 6.1 mm thick hot-rolled sheet. Table 1 describes the

chemical composition of this material. The material was solution-treated at 1050

°C for 1 h and quenched in water at room temperature (25 °C). Then, cylindrical

samples 6.0 mm in diameter were carefully obtained by electric discharge

machining (EDM). Finally, the samples were thermally aged in an electric

furnace at 475 °C for 100, 300, 600, 1100 and 2000 h.

 6

2.2. Microstructure characterization

For the microstructural characterization, the samples were mounted in

polyester cold cure resin, mechanically sanded with up to 2000 grit sandpaper,

polished with a 1.0 μm alumina suspension, and etched with Beraha’s reagent

(80 mL H2O + 20 mL 37% HCl + 1.0 g K2S2O5 + 2.0 g NH5F2), as specified by

the ASTM E407 standard [17]. The resulting microstructures were examined in

an Axiotech Zeiss optical microscope.

The microstructure of the sample thermally aged for 2000 h was also

analyzed by TEM in a FEI Tecnai™ G2 F20 microscope operating at 200 kV

and equipped with a TECHNA X-ray analyzer (EDX - Energy Dispersive X-ray).

The samples were prepared as follows. First, 300 μm thick samples were cut

by EDM. Their thickness was then reduced by sanding using a sequence of

400, 600, and 1200 grit sandpaper. Finally, the samples were cut into 3.0 mm

diameter discs and polished until they were pierced by an electrolytic polishing

solution of 95% CH3COOH + 5% HClO4.

Measurements were also taken with a ferritescope (Fisher Feritscope®

GAB.3D – Fe) to estimate the volume fraction of ferrite in the samples. The

mean and standard deviation values were determined based on ten

measurements of each sample.

2.3. Mechanical properties

The ferrite hardness was measured by means of the Vickers

microhardness test and correlated with the aging time. Indentations were
 7

produced Indentations were produced using a Shimadzu HMV-2 micro

hardness tester with a load of 25 g for 15 s, as recommended by ASTM E384

[18]. under a load of 25 g for 15 s, as recommended by ASTM E384 [18]. The

mean and standard deviation values were determined based on ten

measurements of this phase.

The impact toughness of the aged samples was evaluated based on

Charpy impact tests performed at room temperature, according to ASTM E23

[19]. These tests were performed in triplicate, using a Mohr & Federhaff PSW

30 impact pendulum tester of 300 J and sub-size Charpy V-notch specimens (5

mm x 10 mm x 55 mm). To characterize the fracture mechanisms, the fractured

surfaces of the Charpy V-notch specimens were examined in a Leo Stereoscan

440 scanning electron microscope.

2.4. Corrosion behavior

The corrosion resistance of the samples was evaluated through DL-EPR

tests in a 0.5 M H2SO4 + 0.01 M KSCN solution, at 25 °C. A conventional three-

electrode electrochemical cell composed of a platinum auxiliary electrode and a

satured calomel reference electrode (SCE), connected to a Solartron SI 1287A

potentiostat, was also used. The working electrodes were constructed with the

previously mentioned cylindrical samples (0.283 cm2 of exposed area). Three

measurements were taken of each sample. Polarization scans started 10 min

after immersion of the samples. The potential was scanned in the anodic

direction, from -500 mVSCE to 300 mVSCE, after which the polarization scan was

reversed in the cathodic direction up to -500 mVSCE. A sweep rate of 1.67 mV/s
 8

was applied. The degree of Cr depletion was evaluated in terms of charge ratio

(Qr/Qa)x100, combined with microstructure observation by SEM (FEI Inspect™

S50) after taking the measurements.

In addition, to verify Cr-enriched regions at the ferrite/austenite interfaces

or ferritic grain boundaries resulting from 2000 h of thermal aging, samples

were chemically attacked with 10% oxalic acid solution, applying a current

density of 1 A/cm2 for 20 s, which is known to selectively etch areas with high

chromium content [20].

To compare the corrosion behavior of LDSS 2404 with that of a standard

duplex alloy, samples of a DSS 2205 (chemical composition shown in Table 1)

also supplied by Outokumpu Stainless AB in the form of a hot-rolled sheet were

used for the electrochemical corrosion measurements. The DSS 2205 samples

were extracted and heat-treated in the same way as the LDSS 2404 samples.

3. Results and discussion

3.1. Microstructure

Figure 1 (a) shows a typical optical micrograph of the solution-treated

sample of LDSS 2404. Note that the microstructure comprises a ferritic matrix

(dark phase) and dispersed islands of austenite (bright phase). Also note that

the phases are elongated in the rolling direction. It should be mentioned that the

OM analysis did not reveal significant microstructural changes in the samples

aged at 475 °C for 2000 h, because the α’ phase is very thin (in the order of a

few nm), making it undetectable in this kind of analysis. These results are in

good agreement with the literature, which reports that microstructural changes
 9

in DSS at low temperatures occur at the nanometric scale and are not visible by

OM and/or SEM, requiring the use of higher resolution techniques such as TEM

or even atom probe tomography (APT) to observe them [2,16,21–23].

Figure1 (b) shows a TEM image of the ferritic matrix of a sample of LDSS

2404 aged at 475 °C for 2000 h. Note the mottled contrast (light gray regions),

which originates from compositional fluctuations due to the formation of a Cr-

rich phase (α') and a phase depleted of this element (α) [24–27]. This complex

demixing process is caused by the miscibility gap between Cr and Fe, which

may occur by a nucleation and growth mechanism or through spinodal

decomposition, depending on the temperature and chemical composition

(nature and content of the alloying element) [23,28–31]. The literature also

reports that cold work can change the nature of the phase separation in ferrite

from nucleation and growth to spinodal decomposition [32].

Another clearly visible feature in the TEM micrograph is the presence of

some nanometric precipitates (dark regions), which, according to the EDS

composition analysis (table inserted in Figure), are enriched in Si and Mn.

Although the electron diffraction patterns of these precipitates were not

precisely determined, the results can be taken as an indication that these are G-

phase type precipitates. This assumption is based on the literature [22,27,33],

which reports that this phase is mainly enriched in those elements.

Figure 2 shows the results of ferritescope measurements. Note that the

ferrite content, which in this case represents the magnetic permeability, is

initially close to 48.7% in the solution-treated sample, decreasing continuously

throughout aging times of over 600 h until it reaches a mean value of 36.2%.

According to Lo and Lai [34], reductions in the magnetic permeability of DSSs

 10

during spinodal decomposition can be attributed to two factors: (1) the

decomposition of ferromagnetic primary ferrite to paramagnetic Cr-rich α’ phase

and ferromagnetic Fe-rich α phase, which leads to a decrease in the overall

ferromagnetism; and (2) the ferrite morphology resulting from spinodal

decomposition, which hinders the movement of the magnetic domain walls,

decreasing the magnetic permeability.

3.2. Mechanical properties

Figure 3 shows the behavior of hardness and absorbed energy during

the Charpy impact tests of LDSS 2404 as a function of aging time at 475 °C for

up to 2000 h. Because only the ferrite undergoes microstructural changes in

response to increasing aging time at low temperatures, the values of hardness

of the studied material were based on Vickers microhardness measurements

taken in this phase [35,36]. Note that thermal aging at 475 °C promotes

hardening of ferrite, which is directly related to the obstruction of the movement

of dislocations caused by the precipitation of nanometric scale α' phase with

modulated structure [35,37,38]. Also note that ferrite hardness undergoes a

marked increase of approximately 42.51% in the initial hours of aging (<100 h),

and that, with increasing thermal aging time, the ferrite hardness reaches

saturation and remains essentially unchanged for up to 2000h of aging. These

results are in good agreement with those reported by Tavares et al. [14]. The

presence of G-phase in the ferrite also contributes to increase the hardness of

ferrite, but according to Danoix et al. [39], spinodal decomposition has a more

pronounced hardening effect than that caused by G-phase precipitation.

 11

In Figure 3, the Charpy impact test results also indicate that LDSS 2404

shows a significant loss in its ability to absorb energy soon after the first 100 h

of aging and saturates after 300 h at around 8 J, which corroborates the

hardness measurements. Figure 4 shows SEM micrographs of fracture surfaces

of the LDSS 2404 samples (a) solution-treated and (b) thermally aged at 475 °C

for 2000 h. Note the presence of dimples along the entire length of the fracture

surfaces of the solution-treated sample, which are characteristic of a ductile

fracture. On the other hand, cleavage planes that are characteristic of a brittle

fracture are visible throughout the fracture surface of the sample aged for up to

2000 h, suggesting that the mechanism of brittle fracture became dominant.

The presence of cleavage planes is a result of α’ phase precipitation, as is the

presence of G-phase in the ferritic matrix, reducing the mobility of dislocations

and embrittling the material. According to Chandra et al. [35], embrittlement of

the ferritic matrix (due to the formation of α’ phase) has a strong influence on

the fracture mode of the austenite, causing shearing of the austenite bonds

between the cleavage planes.

3.3. Corrosion behavior

Figure 5 shows the DL-EPR curves obtained in 0.5 M H2SO4 + 0.01 M

KSCN solution of the solution-treated LDSS 2404 sample and the DSS 2205

sample thermally aged at 475 °C for 2000 h. As can be seen, the samples of

both materials thermally aged for 2000 h have a reactivation peak in the

cathodic scan. However, this peak is much higher in DSS 2205. The peak that

appears in the cathodic scan of DSSs has been attributed to the preferential
 12

corrosion attack of Cr-depleted regions (around carbides and nitrides of Cr, σ

phase, α', G and Chi) [21,36–38,40]. A comparison of the curves clearly reveals

that an increase in activation peak current density also took place as a function

of aging time in both materials. According to Chandra and coworkers [35], this

behavior is related to the appearance of Cr-depleted regions resulting from the

evolution of α′ phase.

The variation in the degree of Cr depletion (Qr/Qa)x100 in the solution-

treated and thermally aged samples of LDSS 2404 and DSS 2205 is shown in

Figure 6. As can be seen, significant Cr depletion in LDSS 2404 occurs only

after 1100 h of aging, reaching a magnitude of 4.8% after 2000 h of aging. In

DSS 2205, however, this depletion occurs after 600 h of aging, increasing

substantially until it reaches 43.2% with the increase in aging time to up to 2000

h. These results are in good agreement with those obtained by the ferritescope

measurements of the LDSS 2404, where significant changes in magnetic

permeability generated by the formation of the α' phase are only visible after

1100 h of aging (Figure 2). Nevertheless, it should be pointed out that the

results of DL-EPR tests differ from those obtained by microhardness and

Charpy impact tests. Hence, it can be seen that after only 100 h of aging there

is already a significant increase in the ferrite hardness and a decrease in the

toughness of LDSS 2404. This suggests that the formation of α’ phase has a

stronger impact on the mechanical properties of materials than on their

corrosion resistance, particularly in the first few hours. Figure 6 clearly shows

that the degree of Cr depletion evolves slowly as a result of the separation of α-

α’ phases, and should take place gradually until both phases reach the same

chemical potential [41,42]. However, this phenomenon is faster in DSS 2205

 13

than in LDSS 2404. According to Melo and Magnabosco [20], both α′ phase

formation mechanisms affect corrosion resistance, but in different ways. As the

nucleation and growth process involve the formation of chromium-enriched

nuclei, the adjacent regions of these nuclei are expected to be chromium-

depleted from the early stages of the α′ phase formation process, so that an

immediate impact on corrosion resistance should be observable. On the other

hand, if the α′ phase formation mechanism consists of spinodal decomposition

as the chromium-enriched and Cr-depleted areas are gradually formed, the

impact on corrosion resistance will only become severe after long aging times.

This can be taken as an indication that the mechanism of separation of the α-α'

phases in the two materials under study occurs by spinodal decomposition and

that this separation occurs at a lower rate in LDSS 2404 than in DSS 2205.

Another point that must be considered is the fact that the electrolyte used

in the DL-EPR tests may not be the most suitable one for assessing Cr

depletion in the two materials under study, nor the choice of depassivating

agent and its optimal concentration. All these factors must be kept in mind,

since they significantly affect the sensitivity of the test [11]. The literature

presents several works whose authors used different types of solution to

measure Cr depletion in DSSs aged at low temperatures [4,26,36,43]. Since the

most suitable solution for DL-EPR tests of the newly developed LDSS 2404 has

not yet been reported in the literature, the choice of a 0.5 M H2SO4 + 0.01 M

KSCN solution at 25 °C was based on the works of Chandra et al. [35] and

Iacoviello et al. [21], who successfully studied the low temperature

embrittlement behavior of a DSS 2205 using this solution. In addition, Gao and

coworkers [44] also successfully used this same solution to evaluate the
 14

corrosion behavior of a thermally aged LDSS.

Figure 6 clearly shows the absence of a self-healing process, which has

been reported by some authors in studies of DSSs aged at low temperatures

[40,45,46]. May et al. [45] reported that the corrosion rate of DSS 2205

decreased in 1.7 M FeCl3 solution after thermal aging at 300 and 400 °C for

7000 h, attributing it to the occurrence of self-healing. Tavares et al. [46]

performed DL-EPR tests on DSS 2205 aged between 350 – 550 °C for up to

1000 h, and reported that the self-healing process started after aging for 1000 h

at 475 °C and 500 h at 550 °C. Recently, Wu et al. [40] reported the same self-

healing process in DSS Z3CN20.09M after 1000 h of thermal aging at 475 °C.

The aforementioned authors attributed these changes to the self-healing

mechanism, associating it with the diffusion of Cr, eliminating or reducing the

concentration gradient of this element. However, our DL-EPR results indicate

that there was no decrease in the degree of Cr depletion for up to 2000 h, and

also that the spinodal decomposition of LDSS 2404 seems to begin in the early

stages of α-α’ phase separation, requiring a long aging period at this

temperature to reach completion. These results are in good agreement with

those reported in the literature. Shek et al. [47] established that α-α’ separation

would keep on developing even after 10000 h of annealing at 500 °C in a cast

DSS. Similar results were reported by Della Rovere et al. [36] and Lo et al. [26],

who evaluated DSS (2205 and 7MoPLUS) aged at low temperatures over a

long period of exposure and did not observe the self-healing process. As

mentioned earlier, α-α' separation can occur by two mechanisms (spinodal

decomposition and/or nucleation and growth). Nevertheless, if the dominant

mechanism is spinodal decomposition (which involves uphill diffusion), this self-

 15

healing mechanism is not thermodynamically plausible.

Figures 7 and 8 show the SEM images of samples (a) solution-treated

and (b) thermally aged at 475 °C for 2000 h of LDSS 2404 and DSS 2205,

respectively, after the DL-EPR test. In the solution-treated samples of both

materials, note a light attack in the ferritic matrices (dark gray), while no

significant attack is observed in the austenite phase (light gray). In the samples

of both materials aged for 2000 h, a sharp attack is visible on the ferrite, while

the austenite phase shows no significant dissolution. In the DSS 2205, the

interior and boundaries of the ferrite grains, as well as the phase boundaries,

show intensive corrosion. On the other hand, in the LDSS 2404, this attack is

less severe than in the DSS 2205, which is in good agreement with the results

presented in Figure 6. This highly localized corrosion attack in the ferrite phase

of both materials is caused by local impoverishment of Cr resulting from α-α'

separation [26,36].

In an attempt to clarify doubts about the sensitivity of DL-EPR tests in

terms of the detection of α' phase formation, both materials were subjected to

electrolytic etching with 10% oxalic acid solution, applying a current density of 1

A/cm2 for 20 s. Figures 9 (a) and (b), respectively, show SEM images recorded

after the etching of LDSS 2404 and DSS 2205 samples aged for 2000 h. Again,

much more severe dissolution is visible in the ferritic matrix of the DSS 2205

sample than in that of the LDSS 2404 sample, confirming the DL-EPR test

results.

To further investigate the causes of this dissimilar corrosion behavior of

the two materials, TEM analyses were also made of the DSS 2205 sample aged

for 2000 h. Figure 10 shows a TEM micrograph of the aged ferritic matrix of the
 16

DSS 2205 sample, where a mottled contrast is clearly visible, which is

characteristic of α-α’ phase separation; and also a number of other nanometric

Si and Mn-enriched precipitates (dark regions), which can be taken as G-phase

precipitates [22,23,27,31,33]. Comparing this figure with Figure 1 (b), one can

see that this nanometric precipitation took place in the ferritic matrix of both

materials, but that this phenomenon is much more abundant in DSS 2205,

where it is even possible to note the formation of coarse lines of G-phase

precipitates (dark lines on the micrograph). These results are in good

agreement with the literature, which has demonstrated that a larger amount of

alloying elements such as Mo and Ni contributes to a much faster rate of α-α’

phase separation and G-phase precipitation [22,48].

4. Conclusions

Based on the experimental results, the following conclusions can be drawn:

1. Thermal aging at 475 °C for 2000 h reduces the ferromagnetism of ferrite

in LDSS 2404. This is due to the formation of α' phase, whose behavior

is paramagnetic.

2. The formation of α′ phase causes saturation of the ferrite hardness of

LDSS 2404 after 100 h of aging, which is accompanied by a drastic

reduction in the material’s ability to absorb energy.

3. The DL-EPR test results indicate that Cr depletion in LDSS 2404 occurs

only after 1100 h of aging, reaching a magnitude of 5% after 2000 h, and

 17

that the formation of α' phase has a stronger impact on the mechanical

properties (e.g., hardness, toughness) than on the corrosion resistance.

4. The DL-EPR test results also suggest that the mechanism of α-α' phase

separation is spinodal decomposition and that the degradation of

corrosion resistance derived from this phenomenon evolves more slowly

in the ferritic matrix of LDSS 2404 than in DSS 2205.

5. Acknowledgements

The authors gratefully acknowledge CAPES (Brazil’s Federal Agency for

the Support and Improvement of Higher Education), PPGCEM/UFSCar

(Postgraduate Program in Materials Science and Engineering of the Federal

University of São Carlos) and the Brazilian research funding

agency CNPq (National Council for Scientific and Technological Development –

grant no. 460659/2014-6), for their financial support of this work.

 18

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Figures

Fig. 1 – (a) Typical optical micrograph of solution-treated sample, and (b) TEM image of the

ferritic matrix of the LDSS 2404 sample aged for 2000 h at 475°C.
 26

Fig. 2 – Effect of aging treatment on the ferrite content of LDSS 2404 measured by ferritescope

(scatter bands measured in 10 tests).

 27

Fig. 3 – Mean values of ferrite hardness and energy absorbed during the impact tests of LDSS

2404 as a function of aging time for up to 2000 h at 475 °C.

 28

Fig. 4 – SEM micrograph of the fracture surface of LDSS 2404 after impact testing: (a) solution

treated, and (b) thermally aged at 475 °C for 2000 h.

 29

(a) (b)

Fig. 5 – DL-EPR curves obtained from the solution-treated sample, aged for 2000 h at 475 °C:

(a) LDSS 2404 and (b) DSS 2205.

 30

Fig. 6 – Effect of thermal aging on the degree of Cr depletion [(Qr/Qa) x 100] of LDSS 2404 and

DSS 2205. Scatter bands measured in 3 tests of each sample.

 31

Fig. 7 – SEM images of the surface aspect of LDSS 2404 after DL-EPR tests: (a) solution-

treated and (b) aged at 475 °C for 2000 h.

 32

Fig. 8 – SEM images of the surface aspect of DSS 2205 after DL-EPR tests: (a) solution-treated

and (b) aged at 475 °C for 2000 h.

 33

Fig.9 – SEM micrographs of samples aged at 475 °C for 2000 h, recorded after electrolytic

etching with 10% oxalic acid solution: (a) LDSS 2404 and (b) DSS 2205.
 34

Fig. 10 – TEM images of the ferritic matrix of DSS 2205 sample aged for 2000 h at 475 °C.
 35

Table captions

Table 1 – Chemical composition of LDSS 2404 and DSS 2205 (wt.%).

Material C S N Cr Ni Mn Mo Si Cu P
LDSS 2404 0.023 0.005 0.28 24.36 3.49 2.75 1.60 0.41 0.50 0.021
DSS 2205 0.025 0.005 0.19 22.61 5.83 1.51 3.26 0.44 0.20 0.022