metals

Article
Isothermal Austenite–Ferrite Phase Transformations
and Microstructural Evolution during Annealing in
Super Duplex Stainless Steels
Andrea Francesco Ciuffini * ID , Silvia Barella, Cosmo Di Cecca, Andrea Gruttadauria,
Carlo Mapelli and Davide Mombelli
Department of Mechanical Engineering, Politecnico di Milano, via La Masa 34, 20156 Milano, Italy;
silvia.barella@polimi.it (S.B.); cosmo.dicecca@polimi.it (C.D.C.); andrea.gruttadauria@polimi.it (A.G.);
carlo.mapelli@polimi.it (C.M.); davide.mombelli@polimi.it (D.M.)
* Correspondence: andreafrancesco.ciuffini@polimi.it; Tel.: +39-340-125-3162

Received: 17 July 2017; Accepted: 8 September 2017; Published: 14 September 2017

Abstract: Super Duplex Stainless Steels (SDSSs) are composed of α-ferrite and γ-austenite grains,
the simultaneous presence of which forms an optimal microstructure to achieve the best combination
of mechanical and corrosion resistance properties. Moreover, international quality standards are strict
about the phase fraction ratio. The purpose of this work is the achievement of a better description
of the phase ratio evolution taking place during annealing at 1080 ◦ C in the super duplex stainless
steels F53–S32750 and F55–S32760. The experimental results show a damped sinusoidal trend in the
α/γ phase ratio evolution with the increase of the soaking time of thermal treatment. This can be
described by coupling both the competitive coarsening growth regime and the concept of the local
equilibrium phase transformations, pointing out a good correspondence with the experimental data.
Further, recrystallization phenomena also play a major role. Finally, the additivity character of the
observed processes has been proven.

Keywords: duplex stainless steel; isothermal austenite–ferrite transformation; multicomponent

diffusion; local equilibrium; additivity rule

1. Introduction
Duplex stainless steels are chromium-nickel-iron bi-phased alloys, in which the fraction of the
constituent phases enables the optimization of the phases’ volume. Due to their ferritic-austenitic
bi-phased microstructure, these steel grades are featured by a unique combination of high strength,
toughness, ductility and corrosion resistance, overcoming the standard single-phase stainless steels
(i.e., austenitic grades and ferritic grades).
If compared with the lower alloyed grades, the super duplex stainless steels (SDSSs) are
characterized by a higher pitting corrosion resistance, which is ranked by the Pitting Resistance
Equivalent Number (PREN). The duplex stainless steels featured by a PREN higher that 40 are
indicated as super duplex. Molybdenum, tungsten and nitrogen are the main alloying additions to
increase pitting corrosion performance and they are added in order to achieve a high PREN value [1].
Moreover, copper is added to improve corrosion resistance in acid solutions and to increase plastic
formability, while the higher nickel concentrations enhance impact toughness [2]. On the other hand,
such an increase of the alloying elements makes the microstructure more prone to the precipitation
of the brittle intermetallic phases which is associated to an adverse effect on corrosion resistance and
ductility [1,2].
Nowadays, the applications of duplex and super-duplex stainless steels are increasing
continuously thanks to their outstanding mechanical properties, their corrosion resistance and their

Metals 2017, 7, 368; doi:10.3390/met7090368 www.mdpi.com/journal/metals

Metals 2017, 7, 368 2 of 16

relatively low cost. Their use has grown drastically over the last fifteen years and, no doubt, there is
great potential for a further volume increase, considering the numerous and consistent advantages
offered by duplex stainless steels. This increasing market evolution involves both some consolidated
industrial fields (i.e., oil and gas applications) and newly approached applications such as construction,
desalinization plants and the nuclear power generation industry [3–5].
On the other hand, the growing trend featuring the market of the super-duplex stainless steels is
limited by the precipitation of the brittle detrimental phases that can take place during the forming
and the welding processes. Another undesired phenomenon that can take place during these processes
is the uncontrolled change of the phase balance [6].
The present work has been performed on F53 (Cr 24–26 wt %, Ni 6–8 wt %, Mo 3–5 wt %,
Cu < 0.5 wt %, Mn < 1.2 wt %, Si < 0.8 wt %, C < 0.03 wt %, N 0.24–0.32 wt % and Fe bal.) and F55
(Cr 24–26 wt %, Ni 6–8 wt %, Mo 3–4 wt %, W 0.5–1 wt %, Cu 0.5–1 wt %, Mn < 1 wt %, Si < 1 wt %,
C < 0.03 wt %, N 0.2–0.3 wt % and Fe bal.) super-duplex stainless steels. It aims to describe the
phase ratio evolution during annealing thermal treatment at 1080 ◦ C, which is a typical hot working
temperature for this steel grade. Nowadays, the assessment of such behavior is of significant
importance, because it determines the quality of the products. In detail, standards are strict for
the austenite content fork—the ideal microstructure is 50:50. Moreover, the comprehension of such
a behavior is critical because it allows achievement of the desired microstructure after the forming step
of the steel products or correction by heat treatment of a microstructure which does not fit the standard
requirements. Finally, a deeper understanding of the phase ratio evolution would allow a better set up
of the forming and welding processes, overcoming one of the main limitations affecting the diffusion
of these steel grades [1,6].
The solid state phase transformations and, more precisely, the migration of the transformation
interfaces have been an active field of research for over a century, focusing mainly on low-alloy
steels [7]. However, previous work indicates that the precipitation of austenite in the stainless steel
is comparable with the decomposition of austenite in low-alloy steels, implying that the direction of
the f.c.c. ↔ b.c.c. transformation is irrelevant; thus, the models developed for low-alloy steels can be
adopted in this context [8].
In the duplex stainless steels the phase transformation process is dynamic and its kinetics results
mainly from the interactions between the diffusion fields in the bulk phases and the behavior of both
carbon and alloying elements through the α-ferrite/γ-austenite interface.
The growth of a phase and consequently the interface migration can be treated by the Local
Equilibrium (LE) model. This model considers a constant activity across the interfaces and the phase
transformations are described under the hypothesis that the local equilibrium between the parent and
the growing phases is maintained even at the migrating interfaces.
In the LE model, the interstitial and the substitutional elements partition are considered according
to the local equilibrium assumptions, and this hypothesis implies that the chemical potential of each
species across the interface should be constant, hence:
γ
µα
i = µi (1)
γ
where µαi and µi are the chemical potential of the element i at the interface in the ferrite and the
austenite phase, respectively. The Local Equilibrium assumption at the α/γ interface requires that the
Equation (1) must be fulfilled for each component across the interface at any time.
Then, at the interface the mass balance law must be satisfied:
v
Jiα − Jiγ = ( xγ − xiα ) (2)
Vm i

where Jiα and Jiγ are the diffusion flux of i in the ferrite and austenite phases respectively, v is the
interface migration velocity, Vm corresponds to the molar volume and xiγ and xiα are the molar fractions
Metals 2017, 7, 368 3 of 16

of the element i in the ferrite and the austenite phase, respectively. Thus, in the LE model, it is necessary
to solve Fick’s second law for all the alloying elements i in both the austenite and ferrite phases ϕ:

∂xiϕ (r, t) ∂xiϕ (r, t)

 
1 ∂ k −1 ϕ ϕ
= k −1 r Di ( xi (r, t)) (3)
∂t r ∂r ∂r

where r is the radial coordinate, t is time, k = 1, 2, 3 is the geometry parameter (planar, cylindrical
and spherical, respectively), xiϕ is the mole fraction of i in ϕ, and Diϕ is the diffusion coefficients of the
chemical species in the considered phase, which are dependent on the composition.
The boundary conditions for LE model can be written as:

∂xiϕ (r, t) 


∂r  r=0 =0 (4)
r=L

where r = 0 and r = L signify the left and right boundary, respectively.

The equilibrium mole fractions at the interface in both the austenite and ferrite phases can be
determined at every time step and then the position of the interface can be calculated as a function
of time.
Due to the large difference in the diffusivities of the alloying elements, there are different
partitioning modes that take place during the phase transformations. The situation becomes even more
complex when a third element or further elements are added to the system. A case of particular interest
is when an atom diffuses many orders of magnitude faster or slower than others. The transformation
is controlled by the diffusion, but the rate of reaction can vary widely depending on whether the
atoms are partitioned between the austenite and the ferrite. Also, the occurrence of a solute drag effect
may play a crucial role in the interface mobility. The combination of these parameters results in three
different growing modes: local equilibrium with partitioning (LEP), local equilibrium with negligible
partitioning (LENP), and paraequilibrium (PE).
In detail, Super-Duplex-Stainless-Steels (SDSSs) have a very complex composition and the
interaction between the different atoms is not easy to predict. Indeed, the Fe-C-Ni system can be
seen as a paradigm of the simplest situation, in which the substitutional element has only a weak
interaction with both C and the moving interface. In spite of this simplicity, in the Fe-C-Mo system the
substitutional Mo atom interactions with both C and the moving phase interface (solute drag effect)
are no longer expected to be negligible [7,9–11].
Further, a well-known problem of long standing interest about the formal kinetics is the conversion
of isothermal kinetic data into predictions of the kinetics for various non-isothermal thermal treatments
used in the real processes. This is often accomplished with the help of the additivity rule, which follows
from Equation (5):
Z t
dt
=1 (5)
0 τ ( X0 , T )

where τ( X0 , T ) represents the isothermal transformation time for the transformed fraction X = X0
at a temperature T and t is the total transformation time. Thus, an additive reaction implies that the
total time to reach a special stage of transformation is obtained by adding the fractions formed by
isothermal transformation in each time range and at each temperature until the sum reaches unity.
These phenomena and the isokinetic behavior that can rule the microstructure evolution have
been extensively investigated for years. In spite of these efforts, the subject is still controversial because
a full understanding of the physical limitations of the approach is lacking. Nevertheless, in industrial
practice, isothermal kinetic behavior is frequently of less importance than its behavior during more
complex thermal treatments. Thus, the additivity rule has been widely used in order to predict
the phase transformation kinetics during thermal treatments. As a consequence, both theoretical
and the experimental studies regarding the additivity rule have focused on its validation and on
Metals 2017, 7, 368 4 of 16

the limitations on nucleation, growth and transformation, in order to describe the kinetics of the
transformation [12–14].

2. Experimental Procedure
Metals 2017, 7, 368 4 of 16
Specimens with dimensions of approximately 30 mm × 20 mm × 15 mm were extracted from
F532.and ingots, featuring a 5:1 reduction ratio. A solution treatment at 1300 ◦ C was then
F55 forgedProcedure
Experimental
performed and the holding time was set for all the samples at 60 s per millimeter and the cooling step
Specimens with dimensions of approximately 30 × 20 × 15 mm were extracted from F53 and F55
wasforged
realized by quenching,
ingots, featuring a using stirred ratio.
5:1 reduction water.AThis initial
solution heat treatment
treatment at 1300 has
°C wasbeen performed
then performed in order
to obtain
and thea holding
duplex timestructure
was setcomposed
for all theonly by α-ferrite
samples at 60 s per andmillimeter and eliminating
γ-austenite, anywas
the cooling step previous
secondary
realized phase which could
by quenching, be present
using stirred water.inThis
the tested steels.
initial heat Moreover,
treatment this performed
has been thermal treatment
in order aims
to eliminate
to obtain aany residual
duplex stress
structure and anyonly
composed deformation
by α-ferrite pattern, avoiding eliminating
and γ-austenite, recrystallization phenomena.
any previous
Thissecondary
thermal phase which
treatment could achieving
allows be present a insupersaturation
the tested steels. Moreover,
of γ-former this thermal within
elements treatment theaims
α-ferritic
to eliminate
phase. A holdingany residual stress and
temperature of 1300 ◦ C was chosen
any deformation pattern,toavoiding
avoid any recrystallization
thermodynamic phenomena.
equilibrium
This thermal
between the metaltreatment
matrix allows
and achieving a supersaturation
any secondary phase; theofsoaking
γ-formertimeelements
was within
set as the
60 α-ferritic
s/mm so that
phase. A holding temperature of 1300 °C
a thermal and chemical homogenization would be assured [4]. was chosen to avoid any thermodynamic equilibrium
between the metal matrix and any secondary phase; the soaking time was set as 60 s/mm so that a
Then, when the chemical homogenization was reached, the general chemical composition of the
thermal and chemical homogenization would be assured [4].
tested material was measured by optical emission spectroscopy.
Then, when the chemical homogenization was reached, the general chemical composition of the ◦
A second
tested materialisothermal
was measured annealing treatment
by optical emission was performed on the SDSSs specimens at 1080 C at
spectroscopy.
differentAholding times. This second heat treatment
second isothermal annealing treatment was performed aimed at on
reproducing the temperature
the SDSSs specimens conditions
at 1080 °C at
experienced duringtimes.
different holding the hot-working,
This second heatavoiding
treatment theaimed
precipitation of thethe
at reproducing detrimental
temperature secondary
conditionsphases.
Different holding
experienced times
during the were tested in
hot-working, order to
avoiding thepoint out the of
precipitation microstructural
the detrimental evolution of the tested
secondary phases.
Different
alloys: holding
18, 36, 72, 145,times215,were
285,tested in order
355, 425, 500,to570,
point710,out850,
the 995,
microstructural
1135 s/mm. evolution of the tested
The samples were water
alloys: 18, 36, 72, 145, 215, 285, 355, 425, 500, 570,
quenched at the end of the annealing heat treatment (Figure 1). 710, 850, 995, 1135 s/mm. The samples were water
quenched at the end of the annealing heat treatment (Figure 1).
A third isothermal treatment was realized to refine the collected data, define the local kinetics
A third isothermal
of the microstructure treatment
evolution was
and realized
prove tothe
that refine the collected
behavior of thedata, define
SDSSs the local
during kinetics thermal
annealing of
the microstructure evolution and prove that the behavior of the SDSSs during annealing thermal
treatment follows the additivity rule. The temperature of this treatment was set at 1080 ◦ C for 72 or
treatment follows the additivity rule. The temperature of this treatment was set at 1080 °C for 72 or
145 s per millimeter of the specimen thickness. The cooling was executed by water quench, also in this
145 s per millimeter of the specimen thickness. The cooling was executed by water quench, also in
heat treatment
this (Figure
heat treatment 1). 1).
(Figure

1500
Temperature [°C]

1000

500

0
0 200 400 600 800 1000 1200 1400
Time [s/mm]

Solution TT ATT 18 s/mm ATT 36 s/mm

ATT 72 s/mm ATT 145 s/mm ATT 215 s/mm
ATT 285 s/mm ATT 355 s/mm ATT 425 s/mm
ATT 500 s/mm ATT 570 s/mm ATT 710 s/mm
ATT 850 s/mm ATT 995 s/mm ATT 1135 s/mm
2nd ATT +72 s/mm 2nd ATT +145 s/mm

Figure 1. Diagram representing the thermal treatments parameters.

Figure 1. Diagram representing the thermal treatments parameters.
The resulting specimens were treated for microstructural examination using Beraha’s tint
etching (which selectively etches the ferritic phase) and oxalic acid electrolytic etching, as
recommended by the standard ASTM E407-07. The quantitative metallographic analysis was
performed following the standards to evaluate second-phase contents and grain sizes by automatic
Metals 2017, 7, 368 5 of 16

The resulting specimens were treated for microstructural examination using Beraha’s tint etching
(which
Metals selectively
2017, 7, 368 etches the ferritic phase) and oxalic acid electrolytic etching, as recommended 5 ofby
16
the standard ASTM E407-07. The quantitative metallographic analysis was performed following the
image analysis
standards according
to evaluate to ASTM E1245-13
second-phase contentsand
andASTM
grain E1382-10. Followingimage
sizes by automatic the same procedure,
analysis the
according
aspect
to ASTM ratios of the and
E1245-13 grains and the
ASTM precipitation-free
E1382-10. Following zone (PFZ)procedure,
the same widths werethemeasured. Theoflocal
aspect ratios the
chemical composition analyses were performed using INCA Oxford Instrument (Tubney
grains and the precipitation-free zone (PFZ) widths were measured. The local chemical composition Woods,
Abingdon,
analyses wereOxon OX13 5QX,
performed UK)
using SEM/EDS
INCA measurements
Oxford on the different
Instrument (Tubney phases. Moreover,
Woods, Abingdon, Oxon OX13 the
crystallographic data were acquired through INCA Oxford Instrument (Tubney Woods,
5QX, UK) SEM/EDS measurements on the different phases. Moreover, the crystallographic data Abingdon,
Oxon OX13 5QX,
were acquired UK) SEM/EBSD
through INCA Oxford analyses.
Instrument (Tubney Woods, Abingdon, Oxon OX13 5QX, UK)
SEM/EBSD analyses.
3. Results
3. Results
Checking the general chemical composition through optical emission spectroscopy of the tested
Checking
material after thethesolution
general thermal
chemicaltreatment,
composition through
produced optical
results in emission
accordance spectroscopy of the tested
with the standards. F53
SDSS hadafter
material results
thecomposed of: Fe 61.90
solution thermal wt %, Crproduced
treatment, 25.16 wt %, Ni 6.34
results wt %, Mo 4.58
in accordance wt the
with %, Cu 0.33 wt
standards.
%,
F53Mn 0.81had
SDSS wt results
%, Si 0.57 wt %, Cof:
composed 0.02Fewt % and
61.90 wt N%,0.29 wt %.wt
Cr 25.16 Further,
%, Ni the
6.34chemical
wt %, Mo composition
4.58 wt %,
measured
Cu 0.33 wtfor%, F55
Mn SDSS
0.81 wtresulted:
%, Si 0.57Fe 61.74
wt %, wtC%, Cr wt
0.02 24.63% wtand%,NNi0.29
6.68wt
wt%.%, Further,
Mo 3.86 wtthe%, W 0.73
chemical
wt %, Cu 0.76measured
composition wt %, Mn for0.74
F55wt %, Si
SDSS 0.49 wtFe
resulted: %,61.74
C 0.02wtwt%, %,
Cr N 0.23wtwt
24.63 %,%.
Ni 6.68 wt %, Mo 3.86 wt %,
The
W 0.73 wtsolution
%, Cu 0.76thermal
wt %,treatment
Mn 0.74 wt of %,
theSiSDSSs
0.49 wtformed a microstructure
%, C 0.02 wt %, N 0.23 wt featured
%. by γ-austenite
grains,
Theembedded in α-ferrite
solution thermal treatment matrix
of thethat wasformed
SDSSs supersaturated in γ-stabilizers
a microstructure featured byelements.
γ-austenite A
consequence
grains, embeddedof this supersaturation
in α-ferrite matrix thatwaswasthesupersaturated
segregation ofinγ-stabilizers
γ-stabilizerselements,
elements. resulting in γ-
A consequence
austenite thick plates located
of this supersaturation was theatsegregation
α-grain boundaries, whichelements,
of γ-stabilizers interconnected
resultingwith the γ-austenitic
in γ-austenite thick
grains.
plates located at α-grain boundaries, which interconnected with the γ-austenitic grains.
The equilibrium
equilibrium phase fractionsfractions ratio, at temperatures below the solution thermal treatment
temperature (1300 °C), ◦ C), moved
moved to to the
the ideal
ideal 50:50
50:50 equal
equal proportion
proportion between
between α-ferrite
α-ferrite and
and γ-austenite.
γ-austenite.
This change
changeinin thethe equilibrium
equilibrium acts asacts as driving
driving force forforce forphase
further further phase transformation.
transformation. As a
As a consequence,
consequence, part of obtained
part of the α-ferrite, the α-ferrite,
during obtained during the homogenization
the homogenization heat treatment, heatwas treatment,
converted was into
converted
γ-austeniteinto
via aγ-austenite via a solid state diffusion-controlled
solid state diffusion-controlled reaction, raising thereaction, raising
γ-austenite the of
content γ-austenite
the alloys
content
(Table 1,ofFigures
the alloys
2 and (Table 1, Figures
3). This 2 and 3).isThis
transformation transformation
supported is supported
by the phase diagrams,by bytheseveral
phase
diagrams, by several
computational models computational models andobservations
and by the experimental by the experimental
[8,15]. observations [8,15].

Figure 2. Microstructures of the F55–S32760 samples after the isothermal annealing thermal
Figure 2. Microstructures of the F55–S32760 samples after the isothermal annealing thermal treatment.
treatment.
Metals 2017, 7, 368 6 of 16

Table 1. Phase ratio and aspect ratio of the γ-austenite phase during the isothermal annealing at
Metals 2017, 7, 368 6 of 16
1080 ◦ C.
Table
Metals 2017,1.7,Phase
368 ratio and aspect ratio of the γ-austenite phase during the isothermal annealing at 1080 °C.
6 of 16
Annealing Soaking
0 36 72 145 215 285 355 425 500 570 710 850 995 1135
Times [s/mm]
Annealing
Table Soaking
1. Phase ratio
Phase 0 and aspect
36 ratio
72 of145
the γ-austenite
215 285phase
355during
425 the 500
isothermal
570 annealing
710 at 1080 995
850 °C. 1135
Times [s/mm] 0.39 0.54 0.57 0.55 0.47 0.42 0.62 0.50 0.47 0.53 0.50 0.51 0.50 0.47
Ratio
Phase
F53–S32750
Annealing Soaking 0.39 0.54 0.57 0.55 0.47 0.42 0.62 0.50 0.47 0.53 0.50 0.51 0.50 0.47
Error
Ratio 0.03
0 0.05
36 0.03
72 0.03
145 0.03
215 0.03
285 0.03
355 0.03
425 0.03
500 0.03
570 0.03
710 0.04
850 0.01
995 0.02
1135
Times [s/mm] Aspect
γ Error
F53–S32750 0.03
9.26 0.05
9.08 0.03
10.52 0.03
10.34 0.03
9.63 0.03
6.76 0.03
7.47 0.03
9.11 0.03
9.19 0.03
8.66 0.03
8.89 0.04
9.23 0.01
8.70 0.02
8.97
γPhase
Ratio
Aspect 0.39 0.54 0.57 0.55 0.47 0.42 0.62 0.50 0.47 0.53 0.50 0.51 0.50 0.47
Ratio 9.26 9.08 10.52 10.34 9.63 6.76 7.47 9.11 9.19 8.66 8.89 9.23 8.70 8.97
Ratio
Phase
F53–S32750 Error 0.03
0.36 0.05
0.49 0.03
0.54 0.03
0.54 0.03
0.40 0.03
0.44 0.03
0.54 0.03
0.51 0.03
0.45 0.03
0.52 0.03
0.41 0.04
0.40 0.01
0.44 0.02
0.41
Phase
Ratio
F55–S32760 γ Aspect 0.36 0.49 0.54 0.54 0.40 0.44 0.54 0.51 0.45 0.52 0.41 0.40 0.44 0.41
Ratio
Error 9.26
0.03 9.08
0.02 10.52
0.05 10.34
0.03 9.63
0.00 6.76
0.04 7.47
0.01 9.11
0.04 9.19
0.03 8.66
0.05 8.89
0.04 9.23
0.01 8.70
0.07 8.97
0.02
Ratio
F55–S32760 Error
Aspect
γPhase 0.03 0.02 0.05 0.03 0.00 0.04 0.01 0.04 0.03 0.05 0.04 0.01 0.07 0.02
γ Aspect 9.33
0.36 10.87
0.49 9.17
0.54 11.61
0.54 10.21
0.40 7.78
0.44 8.21
0.54 9.92
0.51 8.38
0.45 9.09
0.52 10.27
0.41 9.56
0.40 9.64
0.44 8.89
0.41
Ratio
Ratio 9.33 10.87 9.17 11.61 10.21 7.78 8.21 9.92 8.38 9.09 10.27 9.56 9.64 8.89
Ratio
F55–S32760 Error 0.03 0.02 0.05 0.03 0.00 0.04 0.01 0.04 0.03 0.05 0.04 0.01 0.07 0.02
γ Aspect
9.33 10.87 9.17 11.61 10.21 7.78 8.21 9.92 8.38 9.09 10.27 9.56 9.64 8.89
Ratio
0.70
content

0.60
0.70
content
γ-austenite

0.50
0.60
γ-austenite

0.40
0.50

0.30
0.40
0 200 400 600 800 1000 1200
0.30 Time [s/mm]
0 200 400 600 800 1000 1200
F53 – S32750 Phase RatioTime [s/mm]
F55 – S32760 Phase Ratio

F53 – S32750 Phase Ratio F55 – S32760 Phase Ratio

Figure 3. SDSSs trends in the phase ratio evolution during the annealing thermal treatment at 1080 °C.
Figure 3. SDSSs trends in the phase ratio evolution during the annealing thermal treatment at 1080 ◦ C.

From 3.a SDSSs

Figure qualitative
trendspoint
in the of view,
phase during
ratio the during
evolution annealing thermal thermal
the annealing treatment two main
treatment processes
at 1080 °C.
From
occured.a qualitative
In the early point
stages,of view,
the duringofthe
generation annealing thermal
Widmanstätten saw-teethtreatment
structures,two main processes
associated with
occured. From
In theaearly
qualitative
Martensitic-shear stages,
nucleipoint
andof
the view,
then during
generation the sympathetic
withofthe annealing thermal
Widmanstätten treatment
saw-teeth
structures, twoplace
main
structures,
took processes
associated
and such with
occured. In thenuclei
transformation
Martensitic-shear early stages,
phenomena
and the
thenwentgeneration
withonthe
until of
theWidmanstätten saw-teeth
drivingstructures,
sympathetic force was structures,
consumed.
took place associated
The such
and thermodynamic with
transformation
Martensitic-shear
driving force was nuclei and
provided by then
the with in
deviation thethe sympathetic
chemical structures,
composition from took
the place equilibrium
phase and such
phenomena went on until the driving force was consumed. The thermodynamic driving force
transformation phenomena
of the supersaturated went
α-matrix. on until thethe
Subsequently, driving force was started,
consumed. The thermodynamic
was provided by the deviation in the chemical γ-nuclei growth
composition from thefollowing the principle of
phase equilibrium of the
driving force was provided
the minimization by the deviation
of the interfacial in the
free-energy andchemical composition
such a γ-nuclei from
growth the on
went phase
andequilibrium
caused the
supersaturated
of
Subsequently,
α-matrix.α-matrix.
the supersaturated
the γ-nuclei
Subsequently,
growth started,
the γ-nuclei
following the principleofof the
grains to coarsen (Figure 4). Since this phenomenon can begrowth
relevantstarted, following
to the grains’ the principle
shape, their aspect
minimization
the of the
ratiominimization
interfacial free-energy
of the interfacial
has been calculated and reported
and
free-energy such
in Table and
a γ-nuclei growth went on and caused
1. such a γ-nuclei growth went on and caused the
the grains
to coarsen
grains(Figure 4). (Figure
to coarsen Since this phenomenon
4). Since can be relevant
this phenomenon to the grains’
can be relevant shape,shape,
to the grains’ their their
aspect ratio has
aspect
been ratio
calculated
has been and reported
calculated in reported
and Table 1. in Table 1.

Figure 4. F53–S32750 SDSSs microstructure optical microscopy at 200× magnification: early stages of
the annealing treatment, 18 s/mm (A) and after longer holding times, 1135 s/mm (B).
Figure 4. F53–S32750 SDSSs microstructure optical microscopy at 200× magnification: early stages of
Figure F53–S32750
the4.annealing SDSSs18microstructure
treatment, optical
s/mm (A) and after microscopy
longer at 200
holding times, × magnification:
1135 s/mm (B). early stages of
the annealing treatment, 18 s/mm (A) and after longer holding times, 1135 s/mm (B).
Metals 2017, 7, 368 7 of 16

Metals 2017, 7, 368 7 of 16

The formation of Widmanstätten γ- austenite occurs between 1200 ◦ C and 650 ◦ C by nucleation
and growth and follows
The formation a C-curve kinetics.
of Widmanstätten This ferrite
γ- austenite tobetween
occurs austenite transformation
1200 °C and 650 °C(α by→ γ) in duplex
nucleation
and growth and follows a C-curve kinetics. This ferrite to austenite transformation
stainless steels is very similar to the transformation from austenite to the proeutectoid ferrite (α→γ) in duplex
(γ→α)
stainless steels islow-alloy
in hypoeutectoid very similar to the steels.
carbon transformation from
Initially, austenite to
γ-austenite the proeutectoid
precipitates at theferrite (γ→α)
ferrite/ferrite
in boundaries
grain hypoeutectoid and low-alloy carbon steels.
grows through Initially, γ-austenite
the Widmanstätten precipitates
morphology at the
into the ferrite/ferrite
interior of the grain
grains.
boundaries and grows through the Widmanstätten morphology into the interior of
Afterwards, austenite also precipitates as intra-granular side-plate islands. The rate of this reaction is the grains.
Afterwards, austenite also precipitates as intra-granular side-plate islands. The rate of this reaction is
very fast and the ferrite decomposition is fulfilled in a few minutes [6].
very fast and the ferrite decomposition is fulfilled in a few minutes [6].
The occurrence of γ-precipitation phenomena during the cooling paths can be excluded, because
The occurrence of γ-precipitation phenomena during the cooling paths can be excluded, because
of the absence of fine nuclei for the longest annealing times. Moreover, even in the early stages of
of the absence of fine nuclei for the longest annealing times. Moreover, even in the early stages of the
the annealing
annealingthermal
thermaltreatment
treatment thethe α-matrix
α-matrix experiences
experiences a lossa of
loss of γ-stabilizer
γ-stabilizer elements,
elements, which iswhich
the is
the driving
drivingforce
forcefor
for the
the γ-precipitation processes.
γ-precipitationprocesses. AsAsthethe soaking
soaking times
times of of
thethe annealing
annealing thermal
thermal
treatment increases, the fine dispersion of γ-nuclei decreases and their larger average
treatment increases, the fine dispersion of γ-nuclei decreases and their larger average size witnesses size witnesses
the the
competitive
competitivecharacter
charactercharacterizing
characterizingthis
thisgrowth
growth stage (Figure5)5)[1,8].
stage (Figure [1,8].

150000
N° γ-nuclei/mm2

100000

50000

0
0 200 400 600 800 1000 1200
Time [s/mm]

F53 – S32750 F55 – S32760

Figure 5. Evolution of the density of γ-nuclei with the increase of the isothermal annealing soaking time.
Figure 5. Evolution of the density of γ-nuclei with the increase of the isothermal annealing soaking time.

The phase ratio tends to reach a different equilibrium value after the application of the solution
The phase
thermal ratio tends
treatment, to reach
since the a different
existence field of equilibrium
the γ-austenite value
wasafter the application
extended by the lower ofannealing
the solution
thermal treatment,
temperature. since the
However, theexistence field stage
intermediate of theofγ-austenite was extended
this transformation by the lower
is characterized by annealing
strong
temperature.
fluctuations However,
in the phasethe intermediate
fractions. stageofofthe
The variation this transformation
phase fraction is not is characterized
linear as a functionby of strong
the
treatmentin
fluctuations temperature as can be expected
the phase fractions. The variationby quasi-equilibrium transformations.
of the phase fraction is not linear Both
as athe analyzed
function of the
SDSSs point out the same trend in the phase ratio evolution during the
treatment temperature as can be expected by quasi-equilibrium transformations. Both the analyzed intermediate stage of the
annealing
SDSSs point outthermal treatment.
the same trendThe phase
in the ratioratio
phase features broad oscillations
evolution during the around the equilibrium
intermediate stage of the
value (Figure 3).
annealing thermal treatment. The phase ratio features broad oscillations around the equilibrium value
This characteristic trend can be split in two contributing factors: a damping term and a
(Figure 3).
sinusoidal term. Actually, the damping term corresponds to the loss of free-energy of the system at
This characteristic trend can be split in two contributing factors: a damping term and a sinusoidal
the equilibrium between the phases, so it is assisted by a long-range diffusion phenomena and it is
term. Actually, the damping term corresponds to the loss of free-energy of the system at the equilibrium
ruled by the thermodynamic aspects. On the other hand, the sinusoidal oscillations are due to the
between the phases, so it is assisted by a long-range diffusion phenomena and it is ruled by the
local phase transformations and the local diffusive processes controlling the short-range diffusion
thermodynamic
kinetics. aspects. On the other hand, the sinusoidal oscillations are due to the local phase
transformations and the local
At the annealing diffusivethe
temperature processes controlling the short-range
phase transformations are solid state diffusion kinetics.
diffusion-assisted
At the annealing temperature the phase transformations are solid state diffusion-assisted
reactions and they are ruled by the diffusion behavior of the alloying elements involved in a complex reactions
andsystem,
they are ruled
such by investigated
as the the diffusion behavior
steels. of the alloying
The transport of α- andelements involved
γ-stabilizers atoms in a complex
plays system,
a prominent
such as the
role investigated
in the steels. The transport
phase transformation reactions.ofIndeed,
α- and γ-stabilizers
these elements atoms
are plays a prominent
subjected to a strongrole in
the partitioning within the reactions.
phase transformation two phasesIndeed,
composingthese theelements
alloys. Therefore, they to
are subjected areacertainly responsible within
strong partitioning for
the two phases composing the alloys. Therefore, they are certainly responsible for the motion by
the motion of the α/γ interfaces. In this case the phase transformations are mainly controlled of the
α/γdiffusive phenomena
interfaces. of the
In this case substitutional
the atoms (Ni asare
phase transformations γ-former
mainlyand Mo as α-stabilizer
controlled for this
by diffusive alloy),
phenomena
which
of the produced the
substitutional largest
atoms (Nidistortion
as γ-former in the
andlattice
Mo (Figure 6).
as α-stabilizer for this alloy), which produced the
largest distortion in the lattice (Figure 6).
Metals 2017, 7, 368 8 of 16

Metals 2017, 7, 368 8 of 16

Related
MetalsRelated
to the interface motion, another relevant phenomenon also occurs: the generation
2017, 7, 368
to the interface motion, another relevant phenomenon also occurs: the generation8 of of 16
a
of a precipitation-free zone (PFZ) in the α-matrix, surrounding the γ-austenitic grains (Figure 7).
precipitation-free zone (PFZ) in the α-matrix, surrounding the γ-austenitic grains (Figure 7). The
The microstructure
Related to the ofinterface
the precipitation-free
motion, anotherzone has phenomenon
relevant a well-defined
alsofront. The
occurs: thegrowth rateofofa the
generation
microstructure of1/3 the precipitation-free zone has a well-defined front. The growth rate of the γ-grains
precipitation-free
γ-grains follows1/3 a t zone (PFZ) indication
kinetics, in the α-matrix,
of the surrounding the γ-austenitic
diffusion-limited competitive grains (Figure (Figure
coarsening 7). The 7).
follows a t kinetics, indication of the diffusion-limited competitive coarsening (Figure 7).
microstructure of the precipitation-free zone has a well-defined front. The growth rate of the γ-grains
follows a t1/3 kinetics, indication of the diffusion-limited competitive coarsening (Figure 7).

Figure 6. Concentration of the chemical elements across the boundary of the α/γ interfaces, in a F55–
Figure 6. Concentration of the chemical elements across the boundary of the α/γ interfaces,
S32760 SDSS annealed for 355 s/mm and etched through Beraha’s tint etching. This solution
Figure 6. Concentration
in apreferentially
F55–S32760 SDSS of thefor
chemical elements
and across
etchedthe boundary of the tint
α/γ interfaces, in a solution
F55–
etchesannealed
the α-ferritic 355 s/mm
phase. through Beraha’s etching. This
S32760 SDSS
preferentially annealed
etches for 355phase.
the α-ferritic s/mm and etched through Beraha’s tint etching. This solution
preferentially
Moreover, etches
the the α-ferritic
oscillating phase. of the phase fraction trend can be related to the local
component
thermodynamic
Moreover, theequilibrium
oscillatingatcomponent
the moving interface and tofraction
of the phase the short-range
trend diffusive phenomena
can be related to thethat
local
Moreover, the oscillating component of the phase fraction trend can be related to the local
can also involve the recrystallization process. Thus, the upper and the lower limits
thermodynamic equilibrium at the moving interface and to the short-range diffusive phenomena that of this oscillating
thermodynamic equilibrium at the moving interface and to the short-range diffusive phenomena that
cantrend
can
are coupled
alsoalso
involve thethe
involve
respectively with process.
recrystallization the short-range the
recrystallization process. Thus,
diffusive
upperphenomena
Thus, the upper andthe
and
and limits
thelower
lower the reorganization
limits of of this
this
of
oscillating
oscillating
crystalline
trend are are architecture
coupled and
respectively its periodicity is due to the diffusive competitive coarsening processes.
trend coupled respectivelywith
withthe
theshort-range
short-range diffusive phenomenaand
diffusive phenomena andthethe reorganization
reorganization of of
crystalline architecture
crystalline architecture and
anditsits
periodicity
periodicityisisdue
dueto
to the
the diffusive competitivecoarsening
diffusive competitive coarsening processes.
processes.
0.8
[Log10 (μm)]

0.7
0.8
[Log10 (μm)]

0.6 PFZ
0.7
(PFZ Thickness/2)

0.5
0.6 PFZ
0.4
Linear
Thickness/2)

0.5
0.3 (PFZ)
0.4
0.2 Linear
0.3 y = 0,311x - 0,286
(PFZ)
R² = 0,9453
Log10

0.1
Log10 (PFZ

0.2 y = 0,311x - 0,286

0
0.1 R² = 0,9453
1 2 3
0 Log10 (Time) [Log10 (s/mm)]
1 2 3
Log10 (Time) [Log10 (s/mm)]
Figure 7. Precipitation-Free Zones identification (in F53–S32750 SDSS thermally annealed for 995
s/mm sample) and its evolution during the annealing thermal treatment.
Figure 7. Precipitation-Free Zones identification (in F53–S32750 SDSS thermally annealed for 995
Figure 7. Precipitation-Free Zones identification (in F53–S32750 SDSS thermally annealed for 995 s/mm
s/mm sample)
Regarding and
the its evolution
lower during
limits of thisthe annealingtrend,
oscillating thermalthe
treatment.
occurrence of recrystallization was
sample) and its evolution during the annealing thermal treatment.
detected via SEM-EBSD analysis. The coincidence site lattice (CSL) model can be used as a standard
Regarding the lower limits of this oscillating trend, the occurrence of recrystallization was
for the characterization of the grain boundary structure of polycrystals.
detected via the
Regarding lower limits
SEM-EBSD of this
analysis. Theoscillating
coincidence trend,
site the occurrence
lattice of recrystallization
(CSL) model can be used as awas detected
standard
via for
SEM-EBSD analysis. The coincidence site lattice (CSL) model
the characterization of the grain boundary structure of polycrystals. can be used as a standard for the
characterization of the grain boundary structure of polycrystals.
Metals 2017, 7, 368 9 of 16

Metals
Metals 2017,
2017, 7,
7, 368
368 99 of
of 16
16
The frequency of occurrence of a peculiar kind of CSL grain boundary is inherently associated
The frequency of
of occurrence of
of aaand
peculiar kind ofof CSL
CSL grain boundary
boundary is inherently associated
with The frequency
the newly occurrence
recrystallized grains peculiar
formskind a preferred grain
crystallographic isorientation
inherently relative
associatedto
with
with the
the newly
newly recrystallized
recrystallized grains
grains and
and forms
forms a
a preferred
preferred crystallographic
crystallographic orientation
orientation relative
relative to
to the
the
the parent grains. CSL boundaries Σ13 for f.c.c. lattices are associated with fast moving boundaries,
parent
parent grains.
grains. CSL boundaries Σ13
Σ13 forfor f.c.c. lattices are
are associated with fast moving boundaries,
testifying to theCSL boundaries
occurrence of nucleation f.c.c. latticesphenomena
and growth associated[16].with fast moving boundaries,
testifying
testifying to the
to the occurrence
occurrence of nucleation
of nucleation and
and growth
growth phenomena
phenomena [16].
[16].
The CSL frequency of occurrence has been determined for γ-precipitates dispersed within the
The
The CSL
CSL frequency
frequency of
of occurrence
occurrence has
has been
been determined
determined for
for γ-precipitates
γ-precipitates dispersed
dispersed within
within the
the
α-ferrite matrix. Thus, the increase in CSL boundaries Σ13 for f.c.c. γ-austenitic precipitates within
α-ferrite
α-ferrite matrix.
matrix. Thus,
Thus, the
the increase
increase in
in CSL
CSL boundaries
boundaries Σ13
Σ13 for
for f.c.c.
f.c.c. γ-austenitic
γ-austenitic precipitates
precipitates within
within α-
α-
α-ferrite grains proves the occurrence of the recrystallization phenomena. Such phenomena take place
ferrite grains
ferrite grains proves the occurrence of the recrystallization phenomena. Such phenomena take place
whenever the proves
γ-austenitethe occurrence
volume fractionof thereaches
recrystallization
a minimum phenomena.
value in itsSuchbroadphenomena take place
oscillation during the
whenever
whenever the
the γ-austenite
γ-austenite volume
volume fraction
fraction reaches
reaches aa minimum
minimum value
value in
in its
its broad
broad oscillation
oscillation during
during
isothermal annealing thermal treatment (Figure 8) [17–19].
the
the isothermal
isothermal annealing thermal treatment (Figure 8)
8) [17–19].
Finally, theannealing
collectedthermal
data ontreatment
the phase(Figure
ratio after [17–19].
the second isothermal annealing at 1080 ◦ C
Finally,
Finally, the collected
the collected data on
data on the phase
the phase ratioratio after
after the second isothermal annealing at 1080
1080 °C
thermal treatment show a robust correspondence with the the second
phase isothermal
fraction annealing
ratio evolution of theatprevious°C
thermal
thermal treatment
treatment show
show a
a robust
robust correspondence
correspondence with
with the
the phase
phase fraction
fraction ratio
ratio evolution
evolution of
of the
the
annealing treatment, not only in the trends but also quantitatively. Thus, the hypothesis of additivity
previous
previous annealing
annealing treatment,
treatment, not
not only
only inin the
the trends
trends but also quantitatively. Thus, the hypothesis of
for the investigated systems is validated (Figure 9). but also quantitatively. Thus, the hypothesis of
additivity
additivity for the investigated systems is validated (Figure 9).
for the investigated systems is validated (Figure 9).

80
80
[%]
content[%]

60
60
γ-austenitecontent
[%]
Σ13[%]

40
40
CSLΣ13

20
γ-austenite

20
CSL

00
00 200
200 400
400 600
600 800
800 1000
1000 1200
1200
Time
Time [s/mm]
[s/mm]

F53
F53 –– S32750
S32750 Phase
Phase Ratio
Ratio [%]
[%] CSL
CSL Σ13
Σ13 [%]
[%]

Figure
Figure 8. Evolution of CSL boundaries Σ13 proving the occurrence of the recrystallization phenomena.
Figure8.8.Evolution
Evolutionof
ofCSL
CSLboundaries
boundaries Σ13
Σ13 proving
proving the occurrence of
the occurrence of the
the recrystallization
recrystallizationphenomena.
phenomena.

0.7
0.7
content
γ-austenitecontent

0.6
0.6
0.5
0.5
γ-austenite

0.4
0.4
0.3
0.3
00 200
200 400
400 600
600 800
800 1000
1000 1200
1200
Time
Time [s/mm]
[s/mm]

F53
F53 –– S32750
S32750 Phase
Phase Ratio
Ratio F53
F53 –– S32750
S32750 Phase
Phase Ratio
Ratio After
After 2nd
2nd ATT
ATT

Figure ◦ C.
Figure 9.
9. Additivity
Additivity hypothesis
hypothesis confirmation
confirmation after
after second
second isothermal
isothermal annealing
annealing at 1080
1080 °C.
at 1080 °C.

4.
4. Discussion
Discussion
In
In this
this work,
work, the
the phase
phase ratio
ratio evolution
evolution during
during thethe annealing
annealing thermal
thermal treatment
treatment was
was investigated
investigated
and its trend was seen
was seen
and its trend was as
seen as an
as an oscillating
an oscillating curve
oscillating curve damped
curve damped
damped to to the
to the equilibrium
the equilibrium value.
value. This trend can
equilibrium value. This trend be
can be
observed even better whenever
whenever the
observed even better whenever the grains’
the grains’ shape
grains’ shape
shape isis taken
is taken into
taken into account.
intoaccount. Indeed,
account. Indeed, the
Indeed, the presence
thepresence
presenceof of γ/γ
ofγ/γ
γ/γ
internal
internal interfaces and the
interfaces and the twinning
twinning of of interfaces
interfaces into
into γ-austenite
γ-austenite crystalline
crystalline grains
grains are caused by
are caused by the
the
coarsening phenomena that have taken place (Figure 10A). However, the formation
coarsening phenomena that have taken place (Figure 10A). However, the formation of the typical of the typical
typical
lamellar
lamellar microstructure
microstructure at
at high
high temperatures
temperatures is is induced
induced by by the
the α/γ
α/γ interface
interface energy,
energy, which
which isis lower
lower
than the α/α and γ/γ grain boundary energies
than the α/α and γ/γ grain boundary energies [6,20]. [6,20].
Metals 2017, 7, 368 10 of 16

lamellar microstructure at high temperatures is induced by the α/γ interface energy, which is lower
than the α/α and γ/γ grain boundary energies [6,20].
Metals 2017, 7, 368 10 of 16

0.70
γ-austenite content

0.50
0.30
0 200 400 600 800 1000 1200
Time [s/mm]

F53 – S32750 AR-Corrected Phase Ratio

F55 – S32760 AR-Corrected Phase Ratio

(B)

Figure
Figure 10.
10. γ/γ
γ/γinternal
internalinterfaces
interfacesand
andtwinning
twinninginterfaces
interfaces into
into γ-austenite
γ-austenite crystalline
crystalline grains,
grains, revealed
revealed
by oxalic acid electrolytic etching, in the F53–S32750 specimen thermally annealed
by oxalic acid electrolytic etching, in the F53–S32750 specimen thermally annealed for 36 for 36 s/mm
s/mm (A);
(A);
SDSSs phaseratio
SDSSs phase ratioevolution
evolutionduring
duringthethe annealing
annealing treatment
treatment at 1080
at 1080 °C, taking
◦ C, taking into account
into account the γ-
the γ-grains
grains
aspect aspect ratio (B).
ratio (B).

As a consequence of the distribution of the γ-austenite grains in the α-ferrite matrix, a deviation
As a consequence of the distribution of the γ-austenite grains in the α-ferrite matrix, a deviation
from the round shape enhances the probability of the impingement among the austenite grains.
from the round shape enhances the probability of the impingement among the austenite grains.
Whenever this phenomenon occurs, the α/γ interfacial energy increases to a higher value featuring
Whenever this phenomenon occurs, the α/γ interfacial energy increases to a higher value featuring
the γ/γ internal interfaces. Therefore, the increase in interfacial energy of the system provides free
the γ/γ internal interfaces. Therefore, the increase in interfacial energy of the system provides free
energy to support the α-ferrite to γ-austenite phase transformation.
energy to support the α-ferrite to γ-austenite phase transformation.
Through simple geometrical considerations, the probability ratio of impingement depends on
Through simple geometrical considerations, the probability ratio of impingement depends on the
the aspect ratio (the ratio between the maximum and the minimum axis of the ellipse approximating
aspect ratio (the ratio between the maximum and the minimum axis of the ellipse approximating the
the grain shape) of the γ-austenitic grains through the relationship expressed by Equation (6).
grain shape) of the γ-austenitic grains through the relationship expressed by Equation (6).
∗( 1)
=Primp =p = √ AR ∗ ( AR + 1) (6)
n n 0∗ ( n 1)
k = imp = = √ (6)
Pr0 p0 ARn ∗ ( AR0 + 1)
where corresponds to the probability of grain impingement, is the perimeter γ-austenite
grains and
where Pr imp corresponds
corresponds to the
to the aspect ratio
probability of the
of grain γ-austenite grains.
impingement, p is the perimeter γ-austenite grains
Combining this equation with the experimental data
and AR corresponds to the aspect ratio of the γ-austenite grains. on the variation of the aspect ratio featuring
the γ-austenite grains, the calculation of the total surface
Combining this equation with the experimental data on the variationenergy variation is of
made
the possible and
aspect ratio
consequently the estimation of the further volume phase transformation can be performed.
featuring the γ-austenite grains, the calculation of the total surface energy variation is made possible Thus, the
distinction betweenthe
and consequently theestimation
influence of of the
grains geometry
further andphase
volume the chemical aspects can
transformation of the
be phase ratio
performed.
evolution is possible. This can be achieved by the introduction of a correction factor =
, calculated as shown in Equation (6), which takes into account the γ-austenitic grain
aspect ratio. The results of phase ratio evolution can be rearranged applying the correction factor
and they point out a sinusoidal damped behavior at the ongoing annealing thermal treatment (Table
1 and Figure 10B).
Metals 2017, 7, 368 11 of 16

Thus, the distinction between the influence of grains geometry and the chemical aspects of the
phase ratio evolution is possible. This can be achieved by the introduction of a correction factor
imp imp
k = Prn /Pr0 , calculated as shown in Equation (6), which takes into account the γ-austenitic grain
aspect ratio. The results of phase ratio evolution can be rearranged applying the correction factor k
and they point out a sinusoidal damped behavior at the ongoing annealing thermal treatment (Table 1
and Figure 10B).
In order to completely define this sinusoidal damped trend of the phase ratio evolution with
the soaking time of the annealing thermal treatment (Figure 3), the different aspects, featuring this
behavior, will be discussed:

1. The damping term is due to the loss of free-energy of the system near the thermodynamic
equilibrium condition and it is associated with the thermodynamic aspects of the phase
transformations induced by this thermal treatment.
On the basis of the observations, the damping term of the phase fraction evolution follows
an Arrhenius-type equation describing the driving force of the α-ferrite transformation into
γ-austenite. The results confirm the lower activation energy of F53 (1.12 J/mol) if compared
with F55 (2.25 J/mol), due to an initial wider deviation from the thermodynamic equilibrium
as consequence of the higher concentration of γ-formers elements, as expected by the chemical
composition standards [21].
Because of the diffusive nature of this phase transformation, it is possible to define a diffusional
relaxation time τ after which the transformation closely approaches the full thermodynamic
equilibrium, defined as:
τ = a2 /D (7)

where a is the radius of the parent phase grains and D is the diffusion coefficient of the
substitutional solute atoms [22].
The explicit formula of D should be reported:
EA
−k
D = D0 e BT (8)

where D0 is a temperature-independent pre-exponential term of diffusivity, k B is referred to

the Boltzmann constant and E A corresponds to the activation energy of the diffusion [21,23].
The values used for the calculations are those reported by F. Ruffini et al. [23].
Calculating D for the motion of Ni atoms in α-ferrite, the faster substitutional element ruling
the studied system, and obtaining the radius of the parent γ-phase grains (a ≈ 30 µm) from
metallographic analysis (Figure 2), it is possible to calculate the diffusional relaxation time
τ = 228 s/mm. The results are in good accordance with the experimental evidence for the longer
soaking times of the annealing thermal treatment (t > 400 s/mm) (Figures 3 and 10B).
2. A robust deviation from the thermodynamic equilibrium and the Arrhenius-type trend of the
phase ratio evolution occurs during the early stages of the annealing treatment. The explanation
of this behavior can be ascribed to the military character of the ongoing γ-austenite nucleation.
This assumes that local phase transformations would be much faster than the overall kinetics
ruling the system, which is characterized by an intrinsically slower diffusion-controlled kinetics.
As consequence of the military character of the ongoing γ-austenite nucleation processes,
the transformation equilibrium is ruled by the local free-energies that exceed the overall
reaction thermodynamic equilibrium (in the present case the supersaturation of α-matrix by
γ-stabilizers elements). A clear picture of these phenomena can be provided by Widmanstätten
precipitation processes: the nucleation is supported by a local supersaturation, generating grain
Metals 2017, 7, 368 12 of 16

boundaries’ saw-teeth structures but the transformation goes on until it is completed in the
α-ferrite grains [24].
This explanation can be supported by the observation of the local γ-nucleation processes,
which are the cause of the fast increase of γ-austenite volume fraction at the early stages of
Metals the
2017,annealing
7, 368 thermal treatment (Figure 11). 12 of 16

Figure
Figure 11.
11. γ-austenite
γ-austenitenucleation processes
nucleation at early
processes stages
at early of the
stages of annealing treatment
the annealing of theofF53–
treatment the
S32750 samples after 0 s/mm (A) and 18 s/mm (B); γ-austenite as grains, allotriomorphs
F53–S32750 samples after 0 s/mm (A) and 18 s/mm (B); γ-austenite as grains, allotriomorphs (γ-All),(γ-All),
Widmanstätten plates
Widmanstätten plates (γ-W)
(γ-W) and
and Martensitic
Martensitic Shear
Shear nuclei
nuclei (γ-MS).
(γ-MS).

3. The
The minima
minima ofofthe theevolution
evolutionofofthe thephase
phase ratio
ratiowith thethe
with increase
increase of the
of thesoaking
soaking timetimeof the
of
annealing
the annealingthermal treatment
thermal are related
treatment to recrystallization
are related phenomena.
to recrystallization In these
phenomena. Incases,
these the γ-
cases,
austenitic grainsgrains
the γ-austenitic show show
a primary recrystallization
a primary recrystallizationas testified by CSL
as testified datadata
by CSL and,and,afterafter
thatthat
the
recrystallization,
the recrystallization,γ-austenite can grow
γ-austenite again.again.
can grow Moreover, in thein
Moreover, literature it is reported
the literature that while
it is reported that
γ-austenite showsshows
while γ-austenite a primary recrystallization,
a primary recrystallization, α-ferrite undergoes
α-ferrite undergoes recovery
recoverydue duetotoits its high
stacking
stacking fault
fault energy
energy (SFE).
(SFE). Indeed,
Indeed, α-ferrite
α-ferrite grains
grains resemble
resemble the annealing
annealing texture of single
phase
phase ferritic
ferritic steels,
steels, without
without revealing
revealing anyany influence
influence performed
performed by by the
the concurrent
concurrent second
second phase.
phase.
So,
So, the retarded
retarded nucleation
nucleation and the reduced dislocation density, due to recovery, essentially
suppress
suppress recrystallization,
recrystallization, whichwhich is not detected for α-ferritic grains (Figure 8) [17–19].
4.
4. The maximaofofthe
The maxima the phase
phase ratio
ratio evolution
evolution related related
to theto the ongoing
ongoing of the annealing
of the annealing thermal
thermal treatment
treatment are related to the local thermodynamic equilibrium at the moving
are related to the local thermodynamic equilibrium at the moving interfaces. This can be described interfaces. This can
be described
using the Local using the Localmodel
Equilibrium Equilibrium
and it has model been and it hasdemonstrated
already been alreadyexperimentally.
demonstrated
experimentally.
This model points out the differences in the diffusive phenomena of the slowof diffusing
This model points out the differences in the diffusive phenomena the slow
diffusing substitutional elements within the Fe-C system. Nickel interactions
substitutional elements within the Fe-C system. Nickel interactions with the moving interface with the movingare
interface
expectedareto beexpected
weak and to be
canweak andbycan
treated thetreated by the localmodel
local equilibrium equilibrium model
associated withassociated with
the negligible
the negligible(LENP)
partitioning partitioning (LENP) and paraequilibrium
and paraequilibrium (PE) models. (PE) On themodels.
otherOn the the
hand, other hand, the
interactions
interactions between molybdenum
between molybdenum and the moving andinterfaces
the moving areinterfaces
much stronger.are muchThis stronger. This can by
can be interpreted be
interpreted by a model
a model including including
the solute the solute
drag effect [10]. Thisdrageffect
effect [10].as
grows This effect grows
a function as a function
of the interface of
motion
the interface motion and, therefore, of the soaking time of the annealing
and, therefore, of the soaking time of the annealing thermal treatment. However, the strong drag thermal treatment.
However,
effect would the strong
result drag effect
in a robust would
increase of the result in a robust
molybdenum increaseat of
concentration thethe
movingmolybdenum
interfaces
concentration at the moving interfaces (Figure 12) [25]. This instance proceeds
(Figure 12) [25]. This instance proceeds up to the complete loss of chemical energy, promoting up to the completethe
loss of chemical energy, promoting the interface motion and, consequently,
interface motion and, consequently, up to the inversion of the α/γ interface motion. up to the inversion
of the α/γ interface motion.
Metals 2017, 7, 368 13 of 16
Metals 2017, 7, 368 13 of 16

Figure 12. Schematic

Figure 12. Schematic representation
representation of
ofthe
thelocal
localdiffusion
diffusionphenomena
phenomenaoccurring
occurringatatthe α/γ interface
theα/γ interface
during
during its motion. A focus on the main solutes (Cr, Ni, Mo) behavior, as described by the Local
its motion. A focus on the main solutes (Cr, Ni, Mo) behavior, as described by the Local
Equilibrium
Equilibrium model,
model, has
has been
beenprovided.
provided.

5.
5. The periodicity
The periodicityofofthetheoscillating
oscillating component
component of the phase
of the fraction
phase evolution
fraction can be
evolution canassociated with
be associated
the diffusive
with competitive
the diffusive coarsening
competitive processes.
coarsening As extrapolated
processes. by the SEM
As extrapolated by line-scans
the SEM (Figure 6),
line-scans
the motion of the α/γ interfaces is the result of the movements of the strong
(Figure 6), the motion of the α/γ interfaces is the result of the movements of the strong partitioned elements,
as Mo (acting
partitioned as α-stabilizer)
elements, and Ni
as Mo (acting as(behaving
α-stabilizer)as and
γ-former). However,
Ni (behaving the strong
as γ-former). partitionthe
However, of
these elements (due to the generated concentration gradients) promotes their
strong partition of these elements (due to the generated concentration gradients) promotes their motion into the
other phase,
motion respectively
into the Mo towards
other phase, γ-austenitic
respectively Mo towardsgrains and γ-nuclei
γ-austenitic and Ni
grains andinto the α-ferritic
γ-nuclei and Ni
matrix.
into theIfα-ferritic
compared with the
matrix. diffusing paths
If compared withoftheatoms the sizes
diffusing of the
paths grains are
of atoms the much larger,
sizes of so the
the grains
motion direction can be always assumed as perpendicular to the α/γ interface.
are much larger, so the motion direction can be always assumed as perpendicular to the α/γ Thus, the motion
direction of
interface. boththe
Thus, themotion
diffusing species
direction ofisboth
the the
same, while the
diffusing direction
species is theof theirwhile
same, diffusive paths is
the direction
opposed
of [10].
their diffusive paths is opposed [10].
Provided
Provided the
the diffusion-controlled
diffusion-controlled nature
natureofofthe
thesolid-state
solid-statetransformation
transformationof of
α-ferrite into
α-ferrite γ-
into
austenite and under the hypothesis of the competitive growth regime and the identification
γ-austenite and under the hypothesis of the competitive growth regime and the identification of
Ni and
of Ni Mo
and Mo asasthe
themain
mainactors
actorsinvolved
involvedininthese
these phenomena,
phenomena, aa complete description of
complete description of the
the
sinusoidal term of the phase evolution can be achieved. The diffusion-controlled
sinusoidal term of the phase evolution can be achieved. The diffusion-controlled competitivecompetitive
coarsening
coarsening kinetic appears modeled
kinetic appears modeled through
through the
the Equation
Equation (9):
(9):
8 γα / Ω 2 (∞) eq
〈 (h R)〉(t)i
−3〈−(h R)〉 =3 = 8Dg Mo γα/γ ΩMo cMo ( ∞∗

)
 (t0 )i 9 9kB T ∗t
γ eq (9)
(9)
8 D γα/γ ΩNi cNi (∞)
2
h R(t)i3 − h R(t0 )i38= γ Ni/ Ω (∞) ∗ t
g

〈 ( )〉 − 〈 ( )〉 = 9kB T ∗
9
where h〈Ri〉 corresponds
where corresponds to
to the
the average
average grain size, D isisthe
graineqsize, thechemical
chemicalinterdiffusivity,
interdiffusivity,γγα/γ is the
e
/ is the
interface energy, Ω is the atomic volume, c (∞) is the solubility of the element in a phase for
interface energy, Ω is the atomic volume, (∞) is the solubility of the element in a phase for a
a system featured by a planar interface, k is the Boltzmann constant, T is the temperature and t
system featured by a planar interface, B is the Boltzmann constant, is the temperature and
is the time. Under the hypothesis of the same value for the growth of the average particle size,
is the time. Under the hypothesis of the same value for the growth of the average particle size,
the system can be solved and the difference in the diffusion rates between Mo atoms, moving
the system can be solved and the difference in the diffusion rates between Mo atoms, moving
into α-ferrite, and Ni atoms, diffusing into γ-austenite, results in a delay in time for Ni atoms to
Metals 2017, 7, 368 14 of 16

into α-ferrite, and Ni atoms, diffusing into γ-austenite, results in a delay in time for Ni atoms to
cover the same diffusion path length. This calculated delay (t = 240.5 s/mm) corresponds also to
a period of the sinusoidal term of the phase fraction ratio evolution, which has been observed by
the experimental observation (t ≈ 250 s/mm) (Figure 3).
The wide difference in the diffusion rates (100 times in α-ferrite than in γ-austenite) is related
to the atomic packing factor of the b.c.c. α-ferritic structure that is lower than the f.c.c.
γ-austenitic arrangement. Another consequence of this diffusive phenomenon, and according
to the diffusion-controlled phase transformation models, is that the α-ferrite to γ-austenite
transformation (α→γ) is approximately 1.9 times faster than the reverse austenite to ferrite
transformation (γ→α) during the initial stages of the transformation. This occurs due to the
absence of soft impingement phenomena (overlap of diffusion fields of the neighboring grains in
the classic diffusion-controlled growth model, which slows the phase transformation kinetics) in
the initial stages of the phase transformations [10].

A further confirmation of the description of these diffusive phenomena has been obtained
considering the growth rate of the precipitation-free zones (PFZs) in the α-matrix surrounding the
γ-austenitic grains (Figure 7). The literature reports that in binary alloys, the growth of the PFZs is
related to the solute depletion, leading to a growth rate that is a function of the square root of the time,
according to the competitive coarsening regime model [26,27].
In this work, the growth rate of the precipitation-free zone around the γ-grains follows a t1/3
kinetics, which indicates a diffusion-limited competitive coarsening (Figure 7). These results indicate
the coupled action of the simultaneous diffusion of both α-stabilizers and γ-formers elements. Thus,
as a matter of fact, the precipitation-free zone is not just the consequence of the solute depletion but it
is also related to the enrichment of α-formers atoms stabilizing the α-ferrite matrix.
Finally, the additivity hypothesis has been confirmed for the annealing thermal treatments
of Super Duplex Stainless Steels. Since the additivity feature implies that overall time to reach
a definite stage of transformation is obtained by adding the fractions of the time to reach this stage
isothermally until the sum reaches unity [12]. The additivity concept has been associated to the
diffusional growth, but the situation becomes much more complicated if the nucleation stage also is
included, since transformations involving both the nucleation and the growth are not isokinetic [13].
In the present study, this statement can be easily confirmed by the evaluation of the phase
fraction ratio and the consistency with the previous results of its evolution during the annealing
treatment. This is also supported by the microstructure evolution processes, since the nucleation stage
is terminated during the heating ramp of the first annealing thermal treatment, consuming the driving
force deriving by the α-matrix supersaturation. Moreover, during the cooling paths, any significant
phase transformation does not occur. Therefore, during the holding time at the annealing temperature,
only the growth phenomena take place in the alloy and the isothermal character of the heat treatment
ensures the additivity of the processes (Figure 9) [13].
The importance of the experimental confirmation of the additivity feature is related to the narrow
fork of the phase fractions required by the quality standards. Under the hypothesis that additivity rule
is valid, it is possible to tune the phase ratio and correct the unsatisfied parameters simply by a further
annealing treatment [12].

5. Conclusions
This work aims to identify the microstructure variation of the studied F53–S32750 and F55–S32760
steels via different thermal treatments usually industrially performed. The main features of the overall
phase transformations occurring in the considered super duplex stainless steels during the annealing
thermal treatment at 1080 ◦ C have been observed and described:
Metals 2017, 7, 368 15 of 16

• The precipitation-free zone surrounding the γ- grains is featured by a growth rate as a function of
t1/3 . This indicates the diffusion-limited competitive coarsening and the coupled action of the
contemporary diffusions of both α-stabilizers and γ-formers elements.
• The evolution of the phase ratio α/γ results in a sinusoidal behavior damped to the equilibrium
γ-austenite volume fraction. As consequence, the transformation process can be decomposed
into two main contributions: the damping term (related to the thermodynamic aspects of the
processes) due to the loss of free-energy of the system, and the sinusoidal oscillations associated
to the diffusive processes in the alloys. This last aspect rules the kinetics of the reaction.
The initial deviation from the thermodynamic equilibrium is caused by the military character of
the α-intragranular γ nucleation.
• The thermodynamic factor is governed by an Arrhenius-type equation, resulting in lower
activation energy for F53–S32750, as expected by the alloy composition. Discrepancies between
the monotonic damping of the free-energy available for the phase transformation processes and
the effective conversion of α-ferrite into γ-austenite are caused by different γ-grains aspect ratios.
The sinusoidal kinetic component of the phase formation is ruled by the diffusive competitive
coarsening processes. The periodicity is controlled by the diffusion rate of the high partitioning
elements (i.e., nickel and molybdenum) in the different phases.
• The changes in the dominant transformation are due to the solute drag effect of Mo on
the moving interfaces, as predicted by Local Equilibrium model, and to the recovery and
recrystallization phenomena.
• The additivity character of the annealing thermal treatment has been proved. This result, coupled
with the assessment of the phase fraction ratio evolution, represents a very powerful tool for the
achievement of the desired and precise phase fraction ratio in the product realization.

Author Contributions: Andrea Francesco Ciuffini conceived and designed the experiments, performed the
experiments, analyzed the data and wrote the paper; Silvia Barella conceived and designed the experiments and
review the paper; Cosmo Di Cecca performed the experiments and analyzed the data; Andrea Gruttadauria conceived
and designed the experiments and review the paper; Carlo Mapelli contributed reagents/materials/analysis tools
and review the paper; Davide Mombelli analyzed the data.
Conflicts of Interest: The authors declare no conflict of interest.

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