Microstructural and corrosion resistance evaluation of UNS S32750 plasma-

nitrided superduplex steel welded joint

Ferdinando Marco Rodrigues Borges 1#, Rafaela Luiz Pereira Santos1#, Valdemar Silva

Leal 2, José Ribeiro dos Santos Júnior 1, Anderson Oliveira Lobo 1*, Romulo Ribeiro

Magalhães de Sousa 1*

1
Materials and Science and Engineering graduate program, UFPI-Federal University of

Piaui, 64049-550, Teresina, Piauí, Brazil.

2
Federal Institute of Education, Science and Technology of Maranhão – IFMA CEP:

65030 – 005, São Luís, MA

#
These authors contributed equally.

*Corresponding authors: Ferdinando Marco Rodrigues Borges. Email:

ferdinando@ifma.edu.br. Romulo Ribeiro Magalhães de Sousa. Email:

romulorms@gmail.com
ABSTRACT

Superduplex stainless steel (SDSS) has ferrite and austenite phases in its microstructure

combining interesting mechanical properties and corrosion resistance oil extraction

industry applications. Welding of these steels should follow well-judged standards,

especially when it comes to applied welding energies. In the extraction of petroleum, wear

occurs between the friction of tools and rocky materials with interior of pipes of the

SDSS. SDSS has poor tribological properties so that they are subject to the above-

mentioned wear. Low temperature plasma nitriding falls within this context in order to

provide a surface layer with excellent wear resistance and without significant loss in

corrosion resistance. Here two nitriding techniques named conventional nitriding (CN)

and cathodic cage nitriding (CCN) were compared to modify SDSS surface. In addition,

the microstructure and the corrosion resistance of welded joint with and without nitriding

were evaluated. Optical microscopy, scanning electron microscopy, X-ray diffraction and

potentiodynamic polarization characterized the welded joint after nitriding. The SDSS

nitrided by CN provided a higher corrosion resistance than the CCN corrosion potential

(EC= equal to -0,06V to CN and -0.22V to CCN). The differences were attributed to the

formation of a diffusion layer composed of expanded austenite and expanded ferrite

which gave passive film more resistant to the corrosive attack of chloride ions.

Keywords: Super duplex stainless steels, plasma nitriding, corrosion resistance.

1. INTRODUCTION

Super-duplex stainless steels (SDSS) are a category of stainless steels that exhibit
austenitic and ferritic microstructural phases in proportions of approximately (50:50)

50% each, due to their chemical composition and heat treatment. It has high Cr content

(24% - 27%) are also characterized by low carbon content (less than 0.03% by weight).

It contains alloying elements such as molybdenum (2.5% - 5.0%), tungsten (0.5% -

2.5%), copper (0.2% - 2.5%) and nitrogen (0.10 % - 0.35%). These steels are used in

locations with aggressive atmospheres that require high corrosion resistance and

excellent mechanical properties (Neto et al., 2016). These metals have wide application

in the petroleum extraction industry, in the following structures: platforms, piping

systems, evaporators, distillers, storage tanks, among others, where the properties

reported above are necessary (Hsieh, et al, 2001). Even with all these qualities

mentioned, these steels are not immune to localized corrosion attacks originating from

tribocorrosion. One example is the extraction of oil in deep water. The rocky material

causes friction in the ducts, removing the passive film, favoring the penetration of

aggressive ions, such as Cl- (chlorides), the main cause of pitting corrosion (César, et

al., 2011).

In soldering the SDSS, the main difficulty is to keep the percentages of the phases close

to 50% and avoid the formation of deleterious phases (precipitates that decrease the

resistance to corrosion) during the cooling. The welding thermal input must conform to

the standard (0.5 to 2.0 kJ / mm) to keep the austenite and ferrite fractions as close as

possible. When the heat generated in the welding is so high, there is time in the cooling

process of formation of deleterious precipitates; and when there are volumetric austenite

fractions of less than 25%, this becomes unacceptable for most industrial applications

because they considerably reduce corrosion resistance (Norsok Standard, 2004). What

happens is that besides chromium, the chemical elements that give greater resistance to

the corrosion are the nickel, the manganese and the nitrogen. These are mainly
concentrated in austenite (γ). Therefore the phase “γ” has greater resistance to corrosion

when compared to ferrite (α). However, the “α”phase has higher mechanical resistance

due to the greater presence of chromium, molybdenum and silicon elements in its

structure. Therefore, it is important to find the closest possible percentage values to

maintain stability of mechanical strength and corrosion (Hsieh et al., 2001). The

chemical composition of the weld is an important feature to be considered, due to its

influence on the microstructure and consequently the mechanical resistance and

corrosion. Usually the solder addition metals have a nickel content between 2-4%

higher than the base metal content, because nickel is a gamogenic element, stabilizer of

the austenite phase (Tavares et al., 2007).

In the case of tribological properties of SDSS, the behavior is not reasonable, that is,

less than desirable hardness and low wear resistance (Neto et al., 2016). This behavior

can be observed in the petroleum industry in the wear caused by the friction of metallic

cables and rocky materials with the inner wall of the tubes. An interesting alternative to

improve the surface hardness of these materials is the use of conventional plasma (CN)

and cathodic cathode (CCN) nitriding. CN promotes the dissociation of nitrogen atoms,

which are ionized and transported at high speeds up to the metal surface. A

characteristic layer is produced by the diffusion of nitrogen on the surface of the metal

and the properties of this surface layer can be modified by varying the parameters of the

process, such as temperature, treatment time and pressure. It has been observed that

plasma nitriding increases surface hardness and wear resistance, but depending on the

temperature used (above 450 ° C), corrosion resistance can be decreased. This fact

occurs due to the precipitation of chromium nitride to the detriment of its migration

from the substrate. The chromium binds to the nitrogen present in the atmosphere of the

reactor forming CrN (Reis & Ii, 2008). Thus, it is necessary to create a hard layer on the
steel surface without compromising corrosion resistance. Generally, the CN of stainless

steel at a temperature of about 380 to 450 ° C has no adverse effects on the corrosion

resistance, due to the formation of a zone of high hardness, resulting from the diffusion

of the nitrogen in the crystalline cross-linked of the austenite, known as the γNphase

(expanded austenite) with a cubic face centered structure (FCC) (Sousa et al., 2012).

As we are dealing with welded joints of superduplex steels, the behavior of the nitriding

differs from the nitriding in the metal as received, that is, laminated. The grain structure

of the region of the weld is more refined, there are more grain contours, which favors

the diffusion of the nitrogen in the crystalline lattice. This will result in higher hardness

values in the weld region. In the literature, very rare work on nitriding in welded joints

is observed, especially Alphonsa, et al. (2013), in which the treatment was carried out

on an austenitic steel. However, the study did not address the behavior of nitrided welds

in the face of corrosion, and only conventional nitriding was used.

In this paper, in addition to the conventional plasma nitriding technique, the use of the

cathodic cage (CCN) nitriding technique will also be used. This is a device used to

provide uniformity and greater hardness of deposited layers. There have been many

studies with this artifice in the last decade (period that was created), however, in the

literature, there were no studies that use the cathodic cage in welded joints. At CCN, the

samples are electrically insulated because they are on top of a ceramic disk (alumina). A

voltage source applies a potential difference between the reactor wall (anode) and the

cathodic cage (cathode). Atoms are plucked from the surface of the cage and combined

with the reactive gas in the plasma atmosphere, forming compounds that attach to the

surface of the sample. The main advantage of CCN is the formation of a uniform layer,

regardless of the size and geometry of the sample used (Sousa, 2007). Based on the

above information, mainly in what CN and CCN can provide to the weld in terms of
tribological properties and resistance to corrosion, and the shortage of nitrided welded

joints, this work has the objective of evaluating the microstructure and the corrosion

resistance of welded joints with and without nitriding.

2. EXPERIMENTAL PROCEDURE

2.1 Materials and Methods

The base material used in this work was the superduplex stainless steel (UNS S32750)

with filler wire (ER 2594). Details of the chemical compositions of the base metal and

file wire are given in Table 1.

The welding was accomplished by the MIG-MAG proceeding (Metal inert gas/ Metal

active gas) by surface tension transfer (STT), as filler wire was used the ER 2594 and

protective gas (Ar + 2% O2), the pure Argon as purge gas at the root. The weld bead

was made using a PW-455m/STT source linked to a robotic arm HP-20 for automatic

displacement of the welding torch. The welding energies were controlated by

automatized system that has advanced speed control. The welding was performed in two

steps as parameters showed in Table 2.

Standards were also followed Norsok Standard (2004), to avoid phase imbalance and

the appearance of intermetallic precipitates, because in both cases, they could weaken

the welded joint. For the accomplishment of the work, test joints were welded to obtain

full filling of the chamfer with two passes, using the planned welding energies. After

finding the welding parameters, it was transferred to the work plate. This was machined

to the pair, with each part having the following dimensions: 150 x 150 x 6 mm, with V-

wedge (α = 60⁰), root aperture (d) 2 mm and sheet thickness (t) of 6 mm.

Subsequently, the joints were arranged on a copper-joint to enable the integrity of the
root of the weld. After welding, the specimens were drawn in the transversal direction to

the weld bead, dimensions of 20 x 15 x 6mm. They were milled to remove

reinforcement and plan the plate. Posteriorly, the samples were sanded with water sands

(granulometry of 200, 320, 400, 600 and 1200 MESH) and polished on felt disc with

Diamond paste (3m) and lubricating fluid for cleaning and finishing. Lastly, prior to

each nitriding treatment, the samples were cleaned in Acetone P. A. for 10 minutes on

an ultrasound device.

Table 1. Chemical composition of the superduplex stainless steel (UNS S32750) and

filler wire ER2594 (wt.%).

Material Cr Mo Ni C N Mn Si P S Fe

UNS S32750 24.92 3.77 7.05 0.014 0.261 0.76 0.39 0.022 0.001 Bal.

ER 2594 24.92 3.9 9.19 0.011 0.28 0.6 0.46 0.019 0.005 Bal.

Table 2. Parameters of Welding process.

Welding

speed
Type of Medium Medium Welding Energy

pass Current (A) voltage (V) (mm/ s) (KJ/ mm)

Root pass 109 18 3 0.65

Filling
122 15.3 1.33 1.4
pass
2.2 Plasma nitriding process

In the conventional ionic nitriding and cathodic cage, the same equipment was

used, which contains a voltage source with a maximum current of 1500V and 2A,

respectively. The vacuum chamber is cylindrical with 30 cm diameter and 40 cm high,

made of stainless steel. The device called cathodic cage was made with austenitic

stainless steel sheet (AISI 304), 0.8mm thickness, 112mm in diameter, 25mm high and

holes with 8mm in diameter distributed uniformly with distance of 9.2mm between

centers of adjacente holes.

In CCN, the sample is placed on an alumina insulating disk. The Plasma is

formed in the cage, which functions as a cathode (the chamber wall is the anode) and

not directly on the surface of the samples (conventional nitriding), which remain in

floating potential. In both techniques used, firstly occur the previous treatment (called

pre-sputtering) which consists of exposing the samples and cathodic cage to an

atmosphere of composition balanced with 50% H2 + 50% Ar, also have the function of

cleaning the assembly, activating the surface for interaction with the plasma and make

the removing impurities remaining. The nitriding parameters are showed in Table 3.
Table 3. Nitriding parameters.

Plasma Gas mixture Work

Treatment Temperature
Material Nitriding percentage pressure
time (h) (°C)
Type (%) (mbar)

Conventional N2:H2

WJ Nitriding (CN) 20:80

UNS 5 400 2.5

Cathodic Cage
N2:H2
S32750
Nitriding
80:20
(CCN)

WJ – Welded Joint.
*

To certify the phases composition present in the welded joint of AISD UNS

S32750, was used the X-ray diffraction analysis on the diffractometer model

SHIMADZU XRD-6000, with Theta/Theta geometry and with a Pixel 1 D detector,

monochromatic radiation Kα (λ = 1.540598 Å) of copper tube. The records were

collected under the following conditions: voltage = 40kV, current = 30mA, in the

angular range 35-85° (2) with a step of 0.02626 ° (2θ) and count time of 80.15s. The

HighScore Plus version 3.0 software and ICSD database were used to identify the

crystalline phases. The cristalograpfic charts used were 108132, 625865 and 020389.

For microstructural characterization of the base metal (BM), of welding zones, of the

nitrided layers and to calculate the volumetric fractions of ferrrite was used optical

microscopy. The images were captured at the top and weld profile by the Bel Photonics

model MTM-1A equipment.

 All the samples used in optical microscopy were attacked by Behara reagent

(20mL of hydrochloric acid, 80 mL of distilled water and 1g of potassium

metabisulphite) to reveal the microstructure. The ferrite presented a low relief when

compared austenite in contact with Behara attack, because their reactivity that

facilitating the differentiation of these phases. The measurements of layer thickness and

volumetric fractions calculations of ferrite were performed with the support of Image J

software.

In the layer thickness measurements, ten measurements were made along the nitrided

layer from which the arithmetic mean arose. In the volumetric fraction calculation of

ferrite was adopted the increase of 200X. The image was binarized and ten (10) fields

were used per sample to obtain the percentages.

Scanning electron microscopy (SEM, Quanta 250 FEG, FEI) was used to

qualitatively evaluate the microstructure of the welded joint in the upper part, in order to

evaluate the granulation.

The corrosion resistance analysis of the steel was performed by potentiodynamic

polarization technique using a potentiostat (Autolab PGSTAT302N). All

electrochemical tests were carried out using a three-electrode cell, with a graphite

electrode as a counter electrode, a silver/silver chloride (Ag/AgCl) electrode as

reference electrode and the working electrode being the same sample of the welded

plate delimited by a oring with 1 cm2 of area. Samples were kept in open circuit for 1

hour for system stabilization. A solution of 3.5% NaCl was used as electrolyte. The

polarization test was performed with initial scan potential of 0.15V and a scanning

speed of 1 mV/ s. The data was obtained using an open circuit potential and the final

potencial was 1.2V.

3. RESULTS AND DISCUSSION

3.1 Microstructure and Weld Appearance

Fig. 1(a) shows the microstructural analysis of the material as received. It was

observed thepresence of two different types of microstructure, composed by ferrite

lamellae (α - dark phase) and austenite lamellae (γ - lighter phase). Both phases are

arranged in elongated grains in the rolling direction, displaying similar characteristics to

the results found by Pessoa (2015), when conducting research involving the UNS

S32750 steel.

The ferrite volumetric fractions quantification was performed on the base metal,

obtaining an average value of 47.66%. The values found are within the expected range.

This result is consistent because in SDSS the proportion between the phases should be

approximately 50% -50% to ensure that the properties are suitable, as already studied in

(Gunn, 1997). The same samples used in optical microscopy were submitted to the SEM

technique to investigate in detail the material microstructure. In the micrography

obtained by SEM with a magnification of 1000X, Figure 1(b), it is possible to observe

the presence of elongated austenitic islands (γ) in the direction of lamination, the

characteristic microstructure appears in first plane regarding the ferritic matrix, similar

to the presented in literature (Senatore, et al., 2007).

Figure 1. (a) Sample microstructure as received in laminated state, 200x magnification

(b) SEM of the sample as received in laminated state, 1000x magnification.

Figure 2 shows the X-ray diffraction pattern collected from welded joint using a

superduplex steel (WJ UNS S32750). The diffractogram shows the presence of two

distint phases: ferrite- cofirmed by reflexion plans (110), (200) e (211) and austenite

(Fe- ) by reflexion plans (111), (200) e (220).

 (111)
WJ UNS S32750

(110)
600
 −Fe
 −Fe
Intensity (a.u.)

400

(200)

(220)
200

(200)

(211)
0

40 50 60 70 80

2(Degree)

Figure 2. X-ray diffraction pattern of welded joint (WJ).

A series of tests were performed before the welding procedure to find the

parameters that: (i) propitiated the chamfer filled, (ii) good penetration in the root, (iii)

suitable reinforcement of the weld bead and (iv) welding energies within established

limits. As a starting point for the welding values, were used standard of superduplex

steels (Norsok Standard, 2004). It was verified that besides the chamfer fully filled

(Figure 3 (a)) and optimal penetration at the root (Figure 3 (b)), the visual aspect in both

cases are good.

 (a) (b)

Figure 3. (a) Visual aspect of the chamfer filled (b) Visual apspect of the weld root.

After the welding procedure, a sample was removed from the joint for

metallography procedure. With the chemical attack, the heat affected zone (HAZ) can

be easily identified. It was observed on the sides of the fusion zone (FZ), adjacent to the

melting lines, as a region of high ferrite content and coarse granulometry (Figure 4).

The HAZ constituent phases presented are in accordance with Schaeffler's Diagram

(Lippold & Kotecki, 2005). The adjustment of the chemical composition to obtain a

biphasic microstructure can be made from the chromium and nickel equivalent concept.

The diagram relates the chemical composition and microstructure of obtained

stainless-steel. Thus, the present structures were obtained by applying the chromium

and nickel equivalent criteria at room temperature. Chromium equivalent is the set of

elements that stabilize the ferrite phase and the nickel equivalent is the set of elements

that stabilize the austenitic phase (Lima, 2011). From the composition of the material as

received, were calculated the corresponding chromium and nickel equivalent by the

index: [Creq =% Cr +% Mo + 1.5 x% Si + Nb and Nieq =% Ni + 30 x (% N) + 0.5%

Mn], the values obtained were Creq = 29.275% and Nieq = 15.68%.With these results

was verified a duplex structure in the Schaeffler diagram , corroborating with the phases

found in the XRD of Figure 2.

Figure 4. Weld joint microstructure (UNS S32750 steel); 100X magnification.

In the SDSS welding, the fusion zone temperature can reach 1500°C. Above

1300°C the austenite is not stable, wich facilitates the ferritic grains formation

(Modenesi, et al,, 2005). The pronounced growth of the ferritic grains observed in the

HAZ (Figure 4), occurs due to high temperature and cooling rate in the specified region

that has been affected. High temperatures promoted the ferritic grains growth and the
BM
rapid cooling reduced ferrite to austenite transformations. Similar results were observed

by Videira (2016).

The phase transformation of superduplex steels welding can be seen in Figure 5

(Atarmet & King, 1992). It is important to emphasize that both the base metal and the

addition metal have gamagenic (austenite stabilizers) and alhpagenic (ferrite stabilizers)

chemical elements (Pinto, 2009). The consequence is that in the cooling of the metal

there is no complete austenization, coexisting the two phases.

Figure 5. Microstructural Changes in Welded joint of SDSS.

Three different austenite morphologies were observed for the HAZ and fusion

zone with the welding parameters applied. Figure 6(a) shows the structures intragranular

(inside the grain), alotriomorphic (in the grain boundary) and Widmanstätten (getting

out of the grain boundary into the grain). Such morphologies were also observed in

Fonseca (2016).

Ameyama et al. (1992) mentioned in their study, that the austenite

Widmanstätten nucleates separately on the grain boundary surfaces of allotriomic

austenite and grows within delta ferrite grain. This behavior can be explained due the

presence of larger ferritic grains and slow cooling rates, propitiating the emergence of

the three austenite morphologies. When the grain boundary region is already saturated

with allotriomic austenite and the cooling temperature still favors the austenitic

transformation, the Widmanstätten austenite expands into the grain. The observed in the

literature (Ameyama, et al., 1992) also occurred in this work as can be proven by Figure
6 (a). There is benefit in the appearance of this microstructure, because it promotes a

greater resistance to corrosion.

Widmanstätten austenite, resulting from a martensitic reaction, may be

beneficial because the presence of toughness microstructure with a low carbon content,

besides being able to promote a stress relief, depending on the transformation

temperature. The volumetric fraction of ferrite in the HAZ was calculated based on its

full extent. In the case of the fusion zone, top images were used, Figure 6 (b). The

volumetric fraction of ferrite was calculated with the same methodology used for the

base metal, from the average values. Were obtained 53.79% for HAZ and 35.88% for

FZ. These results corroborate with the literature, Norsok Standard (2004), because in

the MIG/MAG processes the volumetric fractions of ferrite tend to be larger in the

HAZ, while in the fusion zone these values tend to be smaller, by the use of filler wire

with a higher percentage of Nickel. It is evident, then, that welding energy has diferente

effects on the microstructural changes undergone in the HAZ when compared to those

occuring in the fusion zone. This behavior can be attributed to high temperature and

consequently lower cooling rates that occur in the FZ, which results in a longer time for

diffusion processes and microstructural changes.

Figure 6. (a) HAZ microstructure showing three austenite morphologies

(Alotriomorphic, Widmanstatten and Intragranular); 200X magnification. (b) SEM of FZ

exhibiting three austenite morphologies (Alotriomorphic, Widmanstatten and

Intragranular); 1000X magnification; (c) CN at 400 ⁰C. (d) CCN at 400 ⁰C; (e) x-Ray

diffraction pattern of nitrided samples and (f) Potentiodynamic polarization curves of

welded joint of UNS S32750 superduplex stainless steel (WJ UNS S32750) and

conventional plasma (CN) and cathodic cage technique (CCN) samples.

The Figure 6 (c) shown the diffusion layer obtained after 5 hours of conventional

treatment (CN 400°C) in a gas atmosphere containing 20% N2 and 80% H2 at 400°C. In

microscopy it is possible to observe the presence of a thin and continuous layer, with a

lighter shade. X-ray diffractogram (Figure 6 (e)) identified planes (111), (110), (200) e

(220) related to the presence of N-Fe (expanded austenite), − Fe (austenite), − Fe

(ferrite) and − Fe (expanded ferrite) phases respectivelly confirming the results of

optical microscopy (Figure 6(c)). It can be inferred that the nitrided layer consists

largely of expanded austenite and expanded ferrite, and the formation of chromium

nitrides (CrN and/or Cr2N) does not occur. The expanded austenite (γN) originates from

the volumetric expansion of the Face Centered Cubic (FCC) crosslinked of the austenite

phase (γ), due to its in nitrogen (N) supersaturation. The intersticial N introduces large

residual compression stresses associated with defects of stacking failures, wich

promotes hardening and can increase the hardness of 4GPa to values close to 14GPa,

without a significant loss of corrosion resistance. The same diffusive process occurs

with the ferrite in its BCC crosslinked (Body Centred Cubic), forming the expanded

ferrite (αN) [1, 2].

 The layers obtained after 5 hours of nitriding treatment using cathodic cage

(CCN 400°C) in a gas atmosphere containing 80% N2 and 20% H2 at 400°C are shown

in Figure 6 (d). Unlike conventional treatment, a coumponds zones was observed when

CCN was used. When CCN is used, the sputtering system is more concentred, due to

the presence of holes in cage, called hollow cathode, propitiating a large ejection of iron

atoms from the holes and more intense interaction with the nitrogen atoms of the

atmosphere of the cage reactor, increasing the performance of the system. As

consequence it can be observed the more intense formation of the Fe3N phase (Sousa et

al., 2012), this behavior can be seen in Figure 6 (e), at angles 2θ = 40,88°, 44,30° and

46,18°, respectivelly.

Thickness measurement of the nitrided layers are shown in Table 4. It should be noted

that failure to record thickness measurements for the compounds zone in the

conventionally treated sample does not imply that they do not exist. Irregular formation

and very thin thickness of the Fe3N phase may be occured in the CN treatment,

however, this fact may not have been verified by the technique used.

Table 4. Average thickness of nitrited layers (CN – Conventional Nitriding; CCN –

Cathode Cage Nitriding).

Nitreted layer

Treatment/ Compounds Diffusion (Compounds Zone +

Temperature zone (µm) zone (µm) Diffusion Zone (µm)) /

Standard deviation

CN 400 ⁰C - 6.22 6.22 ± 0.09

CCN 400 ⁰C 1.94 1.46 3.40 ± 0.07

 Figure 6 (f) shows the polarization curves obtained in 3.5% NaCl solution for a

superduplex stainless steel weld joint without nitriding, conventional plasma and

cathodic cathodic alloys. The sample curves show well defined active, passive and

transpassive dissolution regions.

The slope of the curve with respect to the axis of the current density in the

passivation region of the sample without nitriding is smaller than that of the nitrided

samples. This behavior is related to the presence of the chromium oxide film that

naturally appears in the stainless steels in contact with the atmosphere. Taking into

account that the weld region presented a high percentage of austenite, this contributed to

the high corrosion resistance. It is then considered that the intentional solder energy

used corroborated to these large formations of the austenite phase and consequent

greater resistance to degradation. Among the nitrided samples, the corrosion behavior

obtained by the CN 400°C was higher than the CCN 400°C. The presence of the

expanded austenite and expanded ferrite phases detected in the X-ray diffraction of

Figure 6 (e) played a crucial role, as these phases confer excellent tribological properties

without considerable losses in corrosion resistance (Reis & Ii, 2008). In the literature

(Sousa et al., 2012), the CCN 400°C samples presented higher and more uniform

surface hardness when compared as CN 400°C, however it is observed in Figure 6 (f)

that the corrosion results fell short of the conventionally treated sample. It can be

inferred that the sputtering mechanism of each treatment contributed to this result.

While expanded austenite and expanded ferrite were used in the conventional

treatment because of the prevalence of the nitrogen diffusion mechanism in the steel

melting pot, using cathodic cage the mechanism was sputtering in the cage, consequent

pulling out of Fe atoms, binding of Fe the nitrogen of the nitriding atmosphere and
formation of the iron nitride and condensation of this in the substrate of the steel under

study. This finding of the presence of this Fe3N phase can be seen in the XRD of Figure

6 (e). The iron nitride has a lower corrosion resistance than the phases obtained in the

conventional treatment, besides it has a porous microstructure, facilitating the

penetration of chloride ions of the solution in the layer and triggering the pites

formation (Sousa, 2007). Pite is the type of localized corrosion processed in points or

small areas on the metallic surface producing cavities that present the bottom in an

angular shape and depth generally larger than its diameter (Gentil, 1987)

In the potentiodynamic polarization curves of Figure 6 (f), the potential of pite

(transpassivation) is observed. It is in the anodic part, in the transition between the end

of the passivation region and the beginning of the abrupt increase of the current density,

indicating that there was rupture of the passive film. Table 5 presents the following

values: Corrosion Potential (ECorrosion), Corrosion Current Density (jCorrosion) and Pite

Potential (Epite). In short, the analysis of corrosion resistance of stainless steels, by

means of this electrochemical technique, is not punctual. It uses the values shown in

Table 5, added to the slope of the curve in the passive region, indicating that the greater

the angle between this and the x-axis (corrosion current density) the more passive the

material will be. Considering these assumptions, it is observed that the behavior of

welded joints without nitriding is the most resistant against the attack of aggressive

chloride ions (Cl-) [3].

Table 5. Corrosion Potential Values - ECorrosion, Corrosion Current density - jcorrosion –

Pite Potencial - Epite, extracted from the potentiodynamic polarization curves.

 Samples Ecorrosion (V) jcorrosion (A.cm-2) Epite (V)

WJ S32750 -0.16 4.61 x 10-9 1.03

CN 400 ⁰C -0.06 2.60 x 10-8 0.83

CCN 400 ⁰C -0.22 2.17 x 10-9 0.86

4. CONCLUSIONS

The parameters used in the welding allowed power in the 1.4 kJ / m range. This

yielded ferrite volumetric fractions of 53, 79% in HAZ and 35.88% in FZ. These values

are in cossonance with Norsok Standard.Due to the high percentage of austenite in the

welded joint, it presented a good resistance to corrosion as can be proven by the

potentiodynamic polarization technique. The curve presented is characteristic of

passivation materials; that is, the weld presented films resistant to the chloride ion

attacks of the 3.5% NaCl solution used.

Of the nitrided samples, the one treated conventionally at 400 ° C showed better results

against corrosion. These were higher due mainly to the presence of the expanded

austenite phase detected in x-ray diffraction. Expanded austenite is a phase that provides

high hardness by expanding the CFC structure of the austenite resulting from the

insertion of the nitrogen into the interstices without significant loss in corrosion

resistance. Finally, the cathodic cathodic samples exhibited corrosion resistance lower
than those conventionally treated mainly by the presence of the Fe3N ( - Iron Nitride)

phase in their nitrided layer. It has low corrosion resistance.

5. ACKNOWLEDGMENTS

The authors acknowledge the Welding Laboratory (Mechanical Engineering Course of

the Federal University of Uberlândia) and the Plasma Laboratory and Electrochemistry

of the Federal University of Piauí.

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Figure 1. (a) Sample microstructure as received in laminated state, 200x magnification

(b) SEM of the sample as received in laminated state, 1000x magnification.

 (111)
WJ UNS S32750

(110)
600
 −Fe
 −Fe
Intensity (a.u.)

400
(200)

(220)
200

(200)

(211)
0

40 50 60 70 80

2(Degree)

Figure 2. X-ray diffraction pattern of welded joint (WJ).

Figure 3. (a) Visual aspect of the chamfer filled (b) Visual apspect of the weld root.
Figure 4. Weld joint microstructure (UNS S32750 steel); 100X magnification.

Figure 5. Microstructural Changes in Welded joint of SDSS.

 Figure 6. (a) HAZ microstructure showing three austenite morphologies

(Alotriomorphic, Widmanstatten and Intragranular); 200X magnification. (b) SEM of FZ

exhibiting three austenite morphologies (Alotriomorphic, Widmanstatten and

Intragranular); 1000X magnification; (c) CN at 400 ⁰C. (d) CCN at 400 ⁰C; (e) x-Ray

diffraction pattern of nitrided samples and (f) Potentiodynamic polarization curves of

welded joint of UNS S32750 superduplex stainless steel (WJ UNS S32750) and

conventional plasma (CN) and cathodic cage technique (CCN) samples.

Table 1. Chemical composition of the superduplex stainless steel (UNS S32750) and

filler wire ER2594 (wt.%).

Material Cr Mo Ni C N Mn Si P S Fe

UNS S32750 24.92 3.77 7.05 0.014 0.261 0.76 0.39 0.022 0.001 Bal.

ER 2594 24.92 3.9 9.19 0.011 0.28 0.6 0.46 0.019 0.005 Bal.

Table 2. Parameters of Welding process.

 Welding

speed
Type of Medium Medium Welding Energy

pass Current (A) voltage (V) (mm/ s) (KJ/ mm)

Root pass 109 18 3 0.65

Filling
122 15.3 1.33 1.4
pass

Table 3. Nitriding parameters.

Plasma Gas mixture Work

Treatment Temperature
Material Nitriding percentage pressure
time (h) (°C)
Type (%) (mbar)

Conventional N2:H2

WJ Nitriding (CN) 20:80

UNS 5 400 2.5

Cathodic Cage
N2:H2
S32750
Nitriding
80:20
(CCN)
Table 4. Average thickness of nitrited layers (CN – Conventional Nitriding; CCN –

Cathode Cage Nitriding).

Nitreted layer

Treatment/ Compounds Diffusion (Compounds Zone +

Temperature zone (µm) zone (µm) Diffusion Zone (µm)) /

Standard deviation

CN 400 ⁰C - 6.22 6.22 ± 0.09

CCN 400 ⁰C 1.94 1.46 3.40 ± 0.07

Table 5. Corrosion Potential Values - ECorrosion, Corrosion Current density - jcorrosion –

Pite Potencial - Epite, extracted from the potentiodynamic polarization curves.

Samples Ecorrosion (V) jcorrosion (A.cm-2) Epite (V)

WJ S32750 -0.16 4.61 x 10-9 1.03

CN 400 ⁰C -0.06 2.60 x 10-8 0.83

CCN 400 ⁰C -0.22 2.17 x 10-9 0.86