materials
Article
Effect of Austenitization Temperature on Hot Ductility of
C-Mn-Al HSLA Steel
Peter Prislupcak 1,2, * , Tibor Kvackaj 2 , Jana Bidulska 2 , Pavol Zahumensky 1 , Viera Homolova 3 ,
Lubos Juhar 1 , Pavol Zubko 1 , Peter Zimovcak 1 , Roman Gburik 1 and Ivo Demjan 4






Citation: Prislupcak, P.; Kvackaj, T.;
Bidulska, J.; Zahumensky, P.;
Homolova, V.; Juhar, L.; Zubko, P.;
Zimovcak, P.; Gburik, R.; Demjan, I.
Effect of Austenitization
Temperature on Hot Ductility of
C-Mn-Al HSLA Steel. Materials 2022,
15, 922. https://doi.org/10.3390/
ma15030922
Academic Editor: Thomas Niendorf
Received: 22 December 2021
Accepted: 20 January 2022
Published: 25 January 2022
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
published maps and institutional affil-
iations.
Copyright: © 2022 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Materials 2022, 15, 922. https://doi.org/10.3390/ma15030922
1 Research and Development USSE, U. S. Steel Kosice, s.r.o., Vstupny Areal U. S. Steel Kosice,
044 54 Kosice, Slovakia; pavolzahumensky@sk.uss.com (P.Z.); ljuhar@sk.uss.com (L.J.);
pzubko@sk.uss.com (P.Z.); pzimovcak@sk.uss.com (P.Z.); rgburik@sk.uss.com (R.G.)
2 Department of Plastic Deformation and Simulation Processes, Institute of Materials and Quality Engineering,
Faculty of Materials, Metallurgy and Recycling, Technical University of Kosice, Vysokoskolska 4,
042 00 Kosice, Slovakia; tibor.kvackaj@tuke.sk (T.K.); jana.bidulska@tuke.sk (J.B.)
3 Institute of Materials Research, Slovak Academy of Science, Watsonova 47, 040 01 Kosice, Slovakia;
vhomolova@saske.sk
4 Department of Structural Mechanics, Faculty of Civil Engineering, Technical University of Kosice,
Vysokoskolska 4, 042 00 Kosice, Slovakia; ivo.demjan@tuke.sk
* Correspondence: peterprislupcak@sk.uss.com
Abstract: The article aims to investigate the effect of different austenitization temperatures on the hot
ductility of C-Mn-Al High-Strength Low-Alloy (HSLA) steel. The thermo-mechanical simulator of
physical processes Gleeble 1500D was used for steel hot ductility study. Hot ductility was estimated
by measuring the reduction of area after static tensile testing carried out at temperatures in the range
600 ◦ C to 1200 ◦ C with the step of 50 ◦ C. Evaluation of fracture surfaces after austenitization at
1250 ◦ C and 1350 ◦ C with a holding time of the 30 s showed significant differences in the character of
the fracture as well as in the ductility. The fracture surfaces and the microstructure near the fracture
surfaces of samples at a test temperature of 1000 ◦ C for both austenitization temperatures were
analyzed by Scanning Electron Microscopy (SEM), Light Optical Microscopy (LOM), and AZtec
Feature analysis (particle analysis of SEM). AlN and AlN-MnS precipitates at grain boundaries
detected by the detailed metallographic analysis were identified as the main causes of plasticity
trough in the evaluated steel. Moreover, using Thermo-Calc software, it was found that AlN particles
precipitate from solid solution below the temperature of 1425 ◦ C.
Keywords: HSLA steel; hot ductility; AlN precipitates; ductile fracture; brittle fracture
1. Introduction
The techniques of continuous casting and direct rolling have been introduced and
extended in order to increase process efficiency by saving on energy consumption, human
labor, and production equipment. To ensure these processes are successful, there is a need
to prevent the occurrence of surface defects, especially cracks, which occur quite often
on the slab surfaces. In relation to the improvement of surface quality of continuously
cast steels, it is important to study the hot ductility behavior of steels, considering their
solidifying thermal history together with the crack formation during casting. Increasing
the casting speed and strain rate during straightening can be one of the useful methods to
decrease crack formation shortly after the casting zone [1–6].
Cracks are known to form in three distinct temperature ranges that depend on the duc-
tility of steel: so-called high-temperature zone 1340 ◦ C to solidus, intermediate-temperature
range 800 ◦ C to 1200 ◦ C, and so-called low-temperature zone 700 ◦ C to 900 ◦ C [7].
The high-temperature zone (low strength and ductility) is generally believed to be
due to the presence of liquid films in the interdendritic regions, which do not freeze until
temperatures properly below the solidus are reached [8]. The liquid films contain a high
https://www.mdpi.com/journal/materials
Materials 2022, 15, 922 2 of 14

level of sulfur, phosphorus, and other elements having a segregation coefficient less than
unity. Loss of ductility in the intermediate-temperature zone is strongly dependent on
the Mn/S ratio and the particular thermal history of the steel [7,8]. High Mn and Al
concentrations in steel can significantly change the physicochemical conditions of non-
metallic inclusion formation during steelmaking and casting processes [9]. The number of
MnS inclusions in AHSS steels rises with Al content growth and decreases with N content
growth. The amount of MnS is also affected by the stability of AlN in liquid steel and
declines when AlN can form in liquid steel before solidification starts [10]. The increase
in sulfur from 0.004 to 0.042 wt% was studied in a Fe-30%Mn-9%Al-1%Si-(0.9–1.2)%C-
0.5%Mo steel (wt%). Results of this research show that controlled additions of S may
promote soft and globular MnS that precipitates around AlN during solidification, thus
reducing their negative effect [11]. Thermal history is considerably more complicated
because it includes several variables such as melting/freezing in-situ, reheating from room
temperature, cooling rate, isothermal holding temperature, and holding time [3].
Loss of ductility in the intermediate temperature zone generally decreases with de-
creased cooling rate, decreased holding temperature, and increased holding time. Strain
rate does not appear to have much influence on the ductility [5–7,12].
The low-temperature zone (700 ◦ C to 900 ◦ C) is less known; however, there is a
general agreement that it is usually associated with soluble aluminum in the steel and the
precipitation of AlN at grain boundaries [7,13–17]. The strong nitride-forming element
Al can form a huge amount of AlN inclusions in liquid steel. To control the formation
of AlN inclusions based on the supersaturation of N and Al in liquid alloy steels, it is
required to have correct thermodynamic data for the critical solubility limit of N and AlN
in such steel grades during cooling and solidification [13]. For an explanation of AlN
precipitation, it is also necessary to consider some physical mechanisms: for example, the
precipitate volumetric misfit, the temperature-dependent Young’s modulus, configuration,
temperature, and size-dependent interfacial energies, as well as the ratio between bulk
and grain boundary diffusion [14]. The thermodynamic calculation processed by the
authors of [15] shows that AlN is less stable than Al2 O3 and FeAl2 O4 , and yet nitrides
are frequently found in Fe-Al alloys. The authors further added that for AlN formation,
there must be a region where the oxygen partial pressure is very low. If oxygen has
been consumed in the process of forming oxides, the activity of oxygen in the alloy can
become low enough to allow for the formation of nitrides [15]. The authors of [16] in
their study provided as an example that when the aluminum content is 1.5 wt% in Fe-
Mn-Al-N steel, the critical nitrogen contents for the AlN formation are 0.034, 0.02, and
0.01 wt% at 1548 ◦ C, 1498 ◦ C, and 1448 ◦ C, respectively [16]. Manganese significantly
increases the AlN solubility in liquid steel due to the large effect of manganese on nitrogen
solubility [9]. In light-weight Fe-Mn-Al steels, it was detected that increasing the manganese
content from 2 wt% to 20 wt% increases the total amount of AlN and MnS inclusions by
4–8 times [17]. The addition of titanium and vanadium was reported to be beneficial
in preventing ductility decrease [18,19]. The others authors claimed titanium reduced
ductility [20,21]. However, the optimal Ti/N ratio required to improve the ductility is
still a discussed topic. The hypothesis of embrittlement of steel in the dual-phase region
of austenite-ferrite was expressed by several authors [7,8,22,23]. As two main factors for
embrittlement for this case, the presence of a thin proeutectoid (allotriomorphic) ferrite at
the grain boundaries of austenite and the presence of tensile stresses in the slab surface
shell were determined [22,23]. Dropping the C or Mn to low levels can promote ferrite
formation, leading to very thin troughs, which make it considerably easier to avoid the
problem of transverse cracking [19]. Due to the relatively low temperatures involved, the
third low-ductility zone can be seen to be a factor only in the formation of surface and
subsurface cracks [4–6].
Hot ductility is dependent on austenitic grain size and increases with decreasing grain
size. However, in microalloyed steels, the dependence of hot ductility on grain size is less
pronounced. The reason is the prevailing effect of precipitation of carbo-nitrides of alloying
14, x FOR PEER REVIEW 3 of 14

alloying elements at grain boundaries [19]. Most research was focused on assessing the
Materials 2022, 15, 922 3 of 14
effect of different chemical compositions and different cooling rates on hot ductility, but
the effect of different austenitization temperatures on hot ductility in microalloyed steels
was studied only marginally.
elements at grain boundaries [19]. Most research was focused on assessing the effect of
This work is different
focusedchemical
on finding the relation between austenitization temperature and
compositions and different cooling rates on hot ductility, but the effect of
hot ductility of the C-Mn-Al HSLA steel.
different austenitization temperatures on hot ductility in microalloyed steels was studied
only marginally.
2. Materials and Methods
This work is focused on finding the relation between austenitization temperature and
Experimentalhotwork
ductility
wasofperformed
the C-Mn-Alusing
HSLAthesteel.
material concept of C-Mn-Al HSLA
steel. The chemical composition
2. Materials and of the steel is given in Table 1.
Methods
Experimental work was performed using the material concept of C-Mn-Al HSLA steel.
Table 1. Chemical composition of the C-Mn-Al HSLA steel.
The chemical composition of the steel is given in Table 1.
onent C Mn Table 1. Chemical
Si P of the C-Mn-Al
composition AlHSLA steel.Cr + Mo Nb + Ti
% max. 0.18 max. 2.1 max. 0.14 max. 0.04 max. 0.7 max. 1.0 max. 0.15
Component C Mn Si P Al Cr + Mo Nb + Ti
wt% The temperature
max. 0.18 range
max. 2.1 of plasticity
max. 0.14troughmax. was0.04
defined for max.the
0.7 steel and max.two
1.0 austen- max. 0.15
itization temperatures by Gleeble 1500D. Standard tensile test samples with nominal di-
mensions of ∅10 × 110The mm temperature
taken from range of plasticity
transfer bar (i.e.,trough was definedduring
semi-products for thehot
steelrolling
and two austen-
between roughing itization temperatures
and finishing train ofbyhotGleeble 1500D.
strip mill) inStandard tensile test
the longitudinal samples
direction towith
the nominal
dimensions of ∅10 ×
direction rolling were used in the experiment. Samples were heated with heating rates ofhot rolling
110 mm taken from transfer bar (i.e., semi-products during
between roughing and finishing train of hot strip mill) in the longitudinal direction to the
25 °C·s−1 from ambient temperature to 1200 °C, followed with a heating rate of 10 °C·s−1 to
direction rolling were used in the experiment. Samples were heated with heating rates of
1250 °C. The same25procedure
◦ C·s−1 from was applied
ambient for austenitization
temperature to 1200 ◦ C,temperature
followed withofa1350 °C rate
heating (heat-
of 10 ◦ C·s−1
−1 to 1300
ing rate of 25 °C·sto 1250 ◦ °C and
C. The same 10procedure
°C·s to was
−1 1350applied
°C). Austenitization
for austenitization temperatures
temperatureofof 1350 ◦ C
1250 °C and 1350(heating
°C withrate a soaking
of 25 ◦ Ctime of 1300
·s−1 to 30 s were
◦ C and applied
10 ◦ C·s−before
1 to 1350cooling to the tensile tempera-
◦ C). Austenitization

test temperaturestures
fromof600 ◦
1250°CCtoand 1200
1350 ◦
°C C bywith
cooling rate time
a soaking of 10of°C·s −1
30 s werefollowed
applied bybefore
soakingcooling to the
◦ C to 1200
at the temperature tensile test30
for the temperatures from 600
s. A deformation rate of 10−3·s◦−1Cwas
by cooling
used for rate 10 ◦temper-
alloftest C·s−1 followed by
atures. Per cent ofsoaking at the
reduction oftemperature
area (RA) was for the 30 s.
used toAevaluate
deformation rate of RA
plasticity. 10−3was
·s−1 obtained
was used for all test
temperatures. Per cent of reduction of area (RA) was used
as RA = (A0 − Af) × 100/A0, where A0 and Af are the initial cross-sectional area and the to evaluate plasticity.
final RA was
obtained as RA = (A0 − Af ) × 100/A0 , where A0 and Af are the initial cross-sectional area
cross-sectional area (after rupture) of the tensile sample, respectively, and was given in %.
and the final cross-sectional area (after rupture) of the tensile sample, respectively, and was
The experimentalgiven
schedule
in %. for
Thethe investigation
experimental of thermal
schedule cycles and ductility
for the investigation of thermal is cycles
given and
in ductility
Figure 1. is given in Figure 1.

Figure 1. Heating and cooling

Figure cycleand
1. Heating schedules
cooling are used
cycle for theare
schedules determination of hot ductility.
used for the determination of hot ductility.

To investigate microstructure fracture surfaces

To investigate microstructure and surfaces
fracture the chemistry
and theof phases, of
chemistry Light
phases, Light
Optical
Optical Microscopy Microscopy
(LOM), (LOM),
Scanning Scanning
Electron Electron (SEM),
Microscopy Microscopy (SEM),
X-ray X-ray
analysis analysis (EDX),
(EDX),
and SEM-based AZtec Feature analysis were used. Feature analysis is automated SEM-
based area scanning focused on positioning and identification of particles and features,
 such as nonmetallic inclusions. The morphological and chemical data of the features were
evaluated. The longitudinally cut samples were mounted in conductive resin. The sur-
faces of samples were metallographically prepared and etched with 3% Nital. The area of
5 × 5 mm was scanned closed to the fracture line. The size of smallest identified feature
Materials 2022,was set to 0.86 μm. The chemical composition of the C-Mn-Al HSLA steel was determined
15, 922 4 of 14
using a OBLF QSG 750 analyzer (OBLF, Witten, DE, Germany) by Optical Emission Spec-
tral Analysis. The thermodynamic calculations were performed using Thermo-Calc soft-
ware (version: TCC S-version) AZtec
and SEM-based with commercial thermodynamic
Feature analysis database
were used. Feature TCFE6
analysis [24].
is automated SEM-
basedcalculated
Phase equilibria were area scanning
for focused on positioning
the temperature rangeand identification
400–1600 °C. of particles and features,
such as nonmetallic inclusions. The morphological and chemical data of the features
3. Results were evaluated. The longitudinally cut samples were mounted in conductive resin. The
surfaces of samples were metallographically prepared and etched with 3% Nital. The area
Hot ductilityofwas
5 × evaluated by measuring
5 mm was scanned closed tothe
thereduction of area
fracture line. (RA)
The size of after static
smallest ten- feature
identified
sile testing at temperatures from 600 °C to 1200 °C with 50 °C steps. Two austenitization
was set to 0.86 µm. The chemical composition of the C-Mn-Al HSLA steel was determined
temperatures of 1250
using °C/30
a OBLFsQSGand750
1350 °C/30(OBLF,
analyzer s wereWitten,
applied. The results
DE, Germany) by are plotted
Optical in Spectral
Emission
Figure 2. As can beAnalysis. The Figure
seen from thermodynamic calculations
2, RA values were austenitized
of samples performed using Thermo-Calc
at 1250 °C (red software
line) were higher(version:
compared TCCtoS-version) with commercial
samples austenitized thermodynamic
at 1350 database
°C (blue line). WhereasTCFE6 [24]. Phase
aus-
equilibria were calculated for the temperature range 400–1600 ◦ C.
tenitization at 1350 °C resulted in a decrease in plasticity to 30% at a temperature range of
950 °C to 850 °C,3.austenitization
Results at 1250 °C resulted in a decrease in plasticity to 45% at
850 °C. The most significant difference in ductility was observed at the test temperature
Hot ductility was evaluated by measuring the reduction of area (RA) after static tensile
of 1000 °C. testing at temperatures from 600 ◦ C to 1200 ◦ C with 50 ◦ C steps. Two austenitization
Evaluation of RA for bothofaustenitization
temperatures temperatures
1250 ◦ C/30 s and 1350 ◦ C/30 sdepends on testing
were applied. tempera-
The results are plotted in
tures, which showed
Figurethat
2. curves
As canhad two from
be seen local Figure
minima. Thevalues
2, RA wholeofinterval test temper-at 1250 ◦ C
samplesofaustenitized
atures was divided
(redasline) were higher compared to samples austenitized at 1350 ◦ C (blue line). Whereas
followed:
◦
austenitization at 1350 C resulted in a decrease in plasticity to 30% at a temperature range
• austenitization temperature 1350 °C was described by four temperature zones (Z1–Z4);
of 950 ◦ C to 850 ◦ C, austenitization at 1250 ◦ C resulted in a decrease in plasticity to 45% at
• austenitization ◦temperature 1250 °C was characterized only by three temperature
850 C. The most significant difference in ductility was observed at the test temperature of
zones (Z1–Z3).
1000 ◦ C.

Figure 2. Reduction of area

Figure 2. (RA) vs. test
Reduction temperature
of area (RA) vs. for
testaustenitization
temperature forataustenitization
1250 °C/30 s atand 1350
1250 ◦ C/30 s and
°C/30 s, red and blue lines,
◦ respectively.
1350 C/30 s, red and blue lines, respectively.

The macroscopicEvaluation of RA fortested

view of samples both austenitization temperatures
by a static tensile depends on testing
test at temperature 1000 temper-
atures,
°C is shown in Figure 3. which showed that curves had two local minima. The whole interval of test
temperatures was divided as followed:
• austenitization temperature 1350 ◦ C was described by four temperature zones (Z1–Z4);
• austenitization temperature 1250 ◦ C was characterized only by three temperature
zones (Z1–Z3).
 Materials 2022, 15, 922 5 of 14

4, x FOR PEER REVIEW 5 of 14

Figure 3. Macro-view of samples after hot ductility
The macroscopic test. tested by a static tensile test at temperature 1000 ◦ C
view of samples
is shown in Figure 3.
From macroscopic observation, it is evident that high ductility was observed on the
sample tested at 1250 °C/30 s compared to the sample tested at 1350 °C/30 s. The ductility
of Sample 2 is characterized as limited with the brittle fracture.
The detailed observations of fracture surfaces of Sample 1 and Sample 2 are illus-
trated in Figure 4 and Figure 5, respectively.
Sample 1 (1250 °C/30 s) showed significant stretching and formation of the neck, and
finally at the center of the neck the fracture formed, as is shown in Figure 4. The fracture
mechanism represents the occurrence of dimples, which grow and coalesce up to fast
shear fracture with the formation of cup and cone fracture surface. Dimple fracture indi-
cates ductile high-energy break with a relative good reduction in area. Dimples were dis-
tributedFigure 3. Macro-view
evenly, with the of samples
Figurerandom after hot ductilityafter
distribution
3. Macro-view of samples test.
ofhotdimple sizes (about 20 μm to 200 μm)
ductility test.
oriented longitudinally toFrom the sample
macroscopic
axis, with the exception of theductility
fast fracture, where
From macroscopic observation, it isobservation,
evident that it ishigh
evident that high
ductility was observed wason
observed
the on the
dimplessample
are oriented in the
sample shear
tested direction.
at 1250 ◦ C/30EDX
s spectrum
compared to the analysis
sample from
tested
tested at 1250 °C/30 s compared to the sample tested at 1350 °C/30 s. The ductility at the
1350 surface
◦ C/30 s. of
The the
ductility
dimplesofshowed of Sampleof 2 is6.1
characterized as limited
14.1with theMn;
brittle fracture.
Sample 2the presence
is characterized wt%with
as limited Al and
the brittle wt%
fracture. the nitrogen was under the
The detailed observations of fracture surfaces of Sample 1 and Sample 2 are illustrated
detection limit.
The detailed inobservations of fracture surfaces of Sample 1 and Sample 2 are illus-
Figures 4 and 5, respectively.
trated in Figure 4 and Figure 5, respectively.
Sample 1 (1250 °C/30 s) showed significant stretching and formation of the neck, and
finally at the center of the neck the fracture formed, as is shown in Figure 4. The fracture
mechanism represents the occurrence of dimples, which grow and coalesce up to fast
shear fracture with the formation of cup and cone fracture surface. Dimple fracture indi-
cates ductile high-energy break with a relative good reduction in area. Dimples were dis-
tributed evenly, with the random distribution of dimple sizes (about 20 μm to 200 μm)
oriented longitudinally to the sample axis, with the exception of the fast fracture, where
dimples are oriented in the shear direction. EDX spectrum analysis from the surface of the
dimples showed the presence of 6.1 wt% Al and 14.1 wt% Mn; the nitrogen was under the
detection limit.

(a) (b)

(a) (b)

(c)
Figure 4. Ductile dimpling after
Figure 4. austenitization at 1250
Ductile dimpling after °/30 s and
austenitization test◦temperature
at 1250 1000 ◦ C,
of 1000 °C,ofSEM.
C/30 s and test temperature
(a) 3000×-magnification; (b) (a) 3000×-magnification; (b)
SEM.2500×-magnification; (c)2500
EDX ×-magnification;
spectrum. (c) EDX spectrum.

(c)
Figure 4. Ductile dimpling after austenitization at 1250 °/30 s and test temperature of 1000 °C, SEM.
 and second-phase particles precipitating at grain boundaries. The presence of coarse par-
ticles of second phase at grain boundaries was confirmed at the 3000× magnification. The
particles were distributed along grain boundaries, their shape was plate-like, and their
size was about 1 μm to 2 μm. The EDX analysis spectrum of particle showed the presence
of 27.3 wt% Mn, 18.3 wt% Al, 15.4 wt% S, and 11.0 wt% N. Based on the chemical compo-
Materials 2022, 15, 922 6 of 14
sition of results, it can be assumed that the particles of the second phase found at grain
boundaries were coarse AlN-MnS precipitates.

(a) (b)

(c)
Figure 5. Intergranular
Figure brittle fracture surface
5. Intergranular after austenitization
brittle fracture surface after at 1350 °/30 s and
austenitization test tempera-
at 1350 ◦ C/30 s and test tempera-
ture of 1000 °C, SEM. (a) 25×◦ magnification; (b) 3000× magnification; (c) EDX spectrum of coarse
ture of 1000 C, SEM. (a) 25× magnification; (b) 3000× magnification; (c) EDX spectrum of coarse
AlN-MnS precipitate.
AlN-MnS precipitate.

To confirm grain coarsening

Sample and◦presence
1 (1250 C/30 s) of second-phase
showed particles
significant at grainand
stretching boundaries
formation of the neck,
LOM of the cross-section at fracture line of samples after austenitization temperature
and finally at the center of the neck the fracture formed, as is shown of 1250
in Figure 4. The
°C/30 s and 1350fracture
°C/30 smechanism
was used. The appearance of the fracture line (Figures
represents the occurrence of dimples, which grow 6 and 7) and
and coalesce up to
microstructuresfast
below
shearthem were with
fracture quitethe
different, withofapparent
formation cup and fracturing
cone fractureat coarse aus-
surface. Dimple fracture
tenite boundaries in Figure 7.
indicates ductile high-energy break with a relative good reduction in area. Dimples were
distributed evenly, with the random distribution of dimple sizes (about 20 µm to 200 µm)
oriented longitudinally to the sample axis, with the exception of the fast fracture, where
dimples are oriented in the shear direction. EDX spectrum analysis from the surface of the
dimples showed the presence of 6.1 wt% Al and 14.1 wt% Mn; the nitrogen was under the
detection limit.
Sample 2 (1350 ◦ C/30 s) showed mild stretching and almost no neck formation with a
small reduction in area, as is shown in Figure 5. The fracture was brittle and intergranular
with low energy to break, caused probably by coarsening the former austenite grain and
second-phase particles precipitating at grain boundaries. The presence of coarse particles
of second phase at grain boundaries was confirmed at the 3000× magnification. The
particles were distributed along grain boundaries, their shape was plate-like, and their size
was about 1 µm to 2 µm. The EDX analysis spectrum of particle showed the presence of
27.3 wt% Mn, 18.3 wt% Al, 15.4 wt% S, and 11.0 wt% N. Based on the chemical composition
 Materials 2022, 15, 922 7 of 14

of results, it can be assumed that the particles of the second phase found at grain boundaries
were coarse AlN-MnS precipitates.
To confirm grain coarsening and presence of second-phase particles at grain bound-
aries LOM of the cross-section at fracture line of samples after austenitization temper-
ature of 1250 ◦ C/30 s and 1350 ◦ C/30 s was used. The appearance of the fracture line
Materials 2022, 14, x FOR PEER REVIEW
(Figures 6 and 7) and microstructures below them were quite different, with apparent 7 of 1
Materials 2022, 14, x FOR PEER REVIEW 7 of 1
fracturing at coarse austenite boundaries in Figure 7.

Figure 6. Fracture line after austenitization at ◦1250 °C/30

s and sstesting
and testing at
◦ C,1000 °C, LOM.
Figure6.6.Fracture
Figure Fractureline after
line austenitization
after at 1250
austenitization C/30°C/30
at 1250 at 1000 at
and testing LOM.
1000 °C, LOM.

Figure 7. Fracture line after austenitization at 1350 °C/30 s, and testing at 1000 °C, LOM.
Figure7.7.Fracture
Figure Fracture line
line after
after austenitization
austenitization at ◦1350
at 1350 C/30°C/30
s, ands,testing
and testing
at 1000 at 1000
◦ C, °C, LOM.
LOM.

ToTo reveal the reason for susceptibility to ductility decrease and tendency to brittl
Toreveal
revealthethereason for susceptibility
reason to ductility
for susceptibility decrease and
to ductility tendency
decrease andtotendency
brittle frac-to brittl
fracture
ture formation
formation if the if the
material material
was exposed was to exposed to
austenitization austenitization
temperature of temperature
1350 ◦ C/30 s, of 135
fracture formation if the material was exposed to austenitization temperature of 135
°C/30
SEM s, SEM
and and EDX
EDX analysis analysis
have haveasbeen
been used, shownused, as shown
in Figure in Figure
8. LOM 8. LOM of the cross
of the cross-section
°C/30 s, SEM and EDX analysis have been used, as shown in Figure 8. LOM of the cross
section
at fractureatline
fracture line ofafter
of samples samples after austenitization
austenitization temperature of 1350 ◦ C/30 of
temperature 1350 °C/30 s con
s confirmed
section
the at fracture line ofphase
samples after at austenitization temperature of 1350 °C/30 s con
firmed the presence of the second phase excluded at the grain boundaries.chemical
presence of the second excluded the grain boundaries. Based on Based on chem
firmed the presence
composition from EDX of the second
it canphase excluded atparticle
the grain boundaries. Based on chem
ical composition fromanalysis,
EDX analysis, be it
stated
can bethatstated
the shown
that the in Figure
particle shown 8a was
in Figure 8
ical composition
coarse AlN precipitate. fromThe EDXsizeanalysis,
of the AlN it can be stated
precipitate that the
is about 4 µm,particle
and theshown in Figure 8
shape was
was coarse AlN precipitate. The size of the AlN precipitate is about 4 μm, and the shap
was coarse
plate-like. AlNonprecipitate.
Based Theprecipitation
the results, AlN size of the AlN precipitate
at grain boundaries is has
about 4 μm,
been andtothe shap
detected
was plate-like. Based on the results, AlN precipitation at grain boundaries has been de
be
wastheplate-like.
reason for material
Based on lowtheductility.
results, AlN precipitation at grain boundaries has been de
tected to be the reason for material low ductility.
tected to be the reason for material low ductility.
 section at fracture line of samples after austenitization temperature of 1350 °C/30 s con-
firmed the presence of the second phase excluded at the grain boundaries. Based on chem-
ical composition from EDX analysis, it can be stated that the particle shown in Figure 8a
was coarse AlN precipitate. The size of the AlN precipitate is about 4 μm, and the shape
was15,plate-like.
Materials 2022, 922 Based on the results, AlN precipitation at grain boundaries has been de-
8 of 14

tected to be the reason for material low ductility.

(a) (b)
Materials 2022, 14, x FOR PEER REVIEW 8 of 14
Figure 8. (a) LOM Figure
of cross-section
8. (a) LOMclose to fractureclose
of cross-section line;to(b) EDXline;
fracture spectrum
(b) EDXofspectrum
found coarse AlN
of found coarse
precipitate. AlN precipitate.

To
To define
definethe
theratio
ratiobetween
betweenAlN,
AlN,AlN-MnS,
AlN-MnS,and andthe
theother
otherparticles
particlesfrom
fromthe
theAl+Mn
Al+Mn
subclass, SEM-based AZtec Feature analysis on an area of 5 × 5 mm was
subclass, SEM-based AZtec Feature analysis on an area of 5 × 5 mm was performed. The performed.
The distribution
distribution of non-metallic
of non-metallic particles
particles at the former
at the former austenite
austenite grain boundaries
grain boundaries is
is shown in
shown in Figure 9. The analysis results showed a significant predominance of AlN
Figure 9. The analysis results showed a significant predominance of AlN particles in com- parti-
cles in comparison
parison with other with other AlN-MnS,
found found AlN-MnS,AlMgO,AlMgO, AlN-AlO,
AlN-AlO, and and
AlOAlOininthe
the ratio
ratio
586:203:152:60:2, respectively.
586:203:152:60:2, respectively.

Figure 9.
Figure 9. Distribution
Distributionofofnon-metallic
non-metallicparticles
particlesatat the
the former
former austenite
austenite grain
grain boundaries
boundaries identified
identified on
on the total area of 5 × 5 mm positioned and evaluated by SEM AZtec Feature
the total area of 5 × 5 mm positioned and evaluated by SEM AZtec Feature analysis. analysis.

As can
As can be
be seen
seen in
in Table
Table 22 and
and Figure
Figure 10,
10, the
the particles
particles with
with sizes
sizes within
within 3.01–4.00
3.01–4.00 µm
μm
represents the greatest volume, followed by particles with sizes within 2.01–3.00
represents the greatest volume, followed by particles with sizes within 2.01–3.00 µm, μm, 4.01–
5.00 μm, µm,
4.01–5.00 5.01–10.00 μm,µm,
5.01–10.00 andand
1.00–2.00 μmµm
1.00–2.00 and greater
and greaterthan
than1010μm.
µm.The
Thesize
size of smallest
smallest
identified feature
identified feature was
was set
setto
to0.86
0.86µm.
μm.

Table 2. Morphological and chemical characteristic of Features—ECD—equivalent circular diameter.

Composition of Number of ECD [μm] ECD [μm] ECD [μm] ECD [μm] ECD [μm] ECD [μm] >
Particles Features 1.00–2.00 2.01–3.00 3.01–4.00 4.01–5.00 5.01–10.00 10.01
AlN 586 15 194 286 75 16 0
AlN-MnS 203 7 66 70 42 15 3
AlMgO 152 0 8 25 41 75 3
AlN-AlO 60 0 8 22 21 9 0
 Figure 9. Distribution of non-metallic particles at the former austenite grain boundaries identified
on the total area of 5 × 5 mm positioned and evaluated by SEM AZtec Feature analysis.

As
can be seen in Table 2 and Figure 10, the particles with sizes within 3.01–4.00 μm
Materials 2022, 15, 922 9 of 14
represents the greatest volume, followed by particles with sizes within 2.01–3.00 μm, 4.01–
5.00 μm, 5.01–10.00 μm, and 1.00–2.00 μm and greater than 10 μm. The size of smallest
identified feature Table
was set to 0.86 μm. and chemical characteristic of Features—ECD—equivalent circular diameter.
2. Morphological

Composition
Table 2.Number of ECD
Morphological and [µm] ECD [µm]
chemical characteristic ofECD [µm] ECD [µm]
Features—ECD—equivalent ECD [µm]
circular ECD [µm] >
diameter.
of Particles Features 1.00–2.00 2.01–3.00 3.01–4.00 4.01–5.00 5.01–10.00 10.01
586of Number of 15ECD [μm]
AlN Composition 194 [μm]
ECD ECD286[μm] ECD [μm75 ] ECD [μm] 16ECD [μm] > 0
Particles Features
AlN-MnS 203 7 1.00–2.00 2.01–3.00
66 3.01–4.00
70 4.01–5.00
42 5.01–10.00
15 10.01 3
AlN 586 15 194 286 75 16 0
AlMgO 152 0 8 25 41 75 3
AlN-MnS 203 7 66 70 42 15 3
AlN-AlO AlMgO 60 152 0 0 8 8 22
25 41 21 75 9 3 0
AlO AlN-AlO 2 60 0 0 0 8 220 21 1 9 1 0 0
AlO 2 0 0 0 1 1 0
Total 1003 22 276 403 180 116 6
Total 1003 22 276 403 180 116 6

14, x FOR PEER REVIEW 9 of 14

(a) (b)

(c) (d)
Figure 10. Found features: (a)Found
Figure 10. All; (b) AlN; (c)AlN-MnS;
features: (d)(c)AlN-MnS;
(a) All; (b) AlN; AlN vs. AlN-MnS.
(d) AlN vs. AlN-MnS.

Table 3 and Figure Table

11 3show
and Figure 11 show
calculated molecalculated mole
fractions of fractions of stableindependence
stable phases’ phases’ independence of
temperature
of temperature for the experimental for the experimental material using Thermo-Calc software.
material using Thermo-Calc software. At the temper- At the temperature
of 1517 ◦ C and above, only the liquid phase exists. The following phases are present
ature of 1517 °C and above, only the liquid phase exists. The◦ following◦ phases are present
in the given temperature ranges: from 1517 C to 1485 C, a two phase region with δ-
in the given temperature ranges: from 1517 °C to 1485 °C, a two phase region with δ-ferrite
ferrite and liquid; from 1485 ◦ C to 1484 ◦ C; δ–ferrite, austenite, and liquid; from 1484 ◦ C
and liquid; from 1485 °C ◦to 1484 °C; δ–ferrite,
to 1480 C, austenite and liquid; austenite,
from 1480 and◦ Cliquid;
to 1425from 1484 °C tofrom
◦ C, austenite; 14801425 ◦ C to
°C, austenite and1278
liquid;
◦ C,from
AlN and1480austenite;
°C to 1425
from°C,1278
austenite;
◦ C to 957from
◦ C, 1425
AlN, °C to 1278and
austenite, °C,Ti-nitride;
AlN from
and austenite; from957 C to 894 C, AlN, austenite, Ti-nitride, and NbTi-carbide; from 894 C to 715 ◦ C,
◦
1278 °C to◦ 957 °C, AlN, austenite, and Ti-nitride; from 957 °C to ◦
894
°C, AlN, austenite,AlN,Ti-nitride,
austenite,and NbTi-carbide;
ferrite, from 894
Ti-carbide/nitride, and °C to 715 °C,from
NbTi-carbide; AlN,715 ◦ C to 688 ◦ C, AlN,
austenite,
austenite,and
ferrite, Ti-carbide/nitride, ferrite, Ti-carbide/nitride,
NbTi-carbide; from 715 NbTi-carbide,
°C to 688 °C, andAlN,
cementite; 688 ◦ C to 539 ◦ C,
fromferrite,
austenite,
AlN, ferrite, Ti-carbide/nitride, NbTi-carbide, andto cementite; ◦ 524 ◦ C, AlN,
Ti-carbide/nitride, NbTi-carbide, and cementite; from 688 °C 539 °C, from
AlN,539 C toTi-
ferrite,
ferrite, Cr-carbide
carbide/nitride, NbTi-carbide, and*, cementite;
Ti-carbide/nitride,
from 539 NbTi-carbide,
°C to 524 and°C, cementite;
AlN, ferrite, 524 C to 511 ◦ C,
fromCr-car- ◦

AlN, ferrite, Cr-carbide *, Ti-carbide/nitride, V-carbide, NbTi-carbide, and cementite; and

bide *, Ti-carbide/nitride, NbTi-carbide, and cementite; from 524 °C to 511 °C, AlN, ferrite,
from 511 ◦ C to 400 ◦ C, AlN, ferrite, Cr-carbide *, Ti-carbide/nitride, -carbide, and NbTi-
Cr-carbide *, Ti-carbide/nitride, V-carbide, NbTi-carbide,
carbide. According to the calculations, andtocementite;
AlN starts precipitate and
fromfrom 511 solid
austenite °C solution
to 400 °C, AlN, ferrite, Cr-carbide *, Ti-carbide/nitride, -carbide, and NbTi-carbide. Ac-
cording to the calculations, AlN starts to precipitate from austenite solid solution at 1425
°C. Its amount is relatively stable up to lower temperatures. In addition to AlN, cementite
(M3C) and Cr-carbide * (M7C3) are stable phases at lower temperatures of the investigated
temperature range. MX phases (Ti-carbide/nitride, V-carbide, NbTi-carbide) were calcu-
Materials 2022, 15, 922 10 of 14

at 1425 ◦ C. Its amount is relatively stable up to lower temperatures. In addition to AlN,

cementite (M3 C) and Cr-carbide * (M7 C3 ) are stable phases at lower temperatures of the
investigated temperature range. MX phases (Ti-carbide/nitride, V-carbide, NbTi-carbide)
were calculated as equilibrium phases (see Table 2); however, their amounts are very low.

Table 3. Calculated phase equilibria in temperature range 400–1600 ◦ C.

Phase Equilibria T [◦ C]
AlN, ferrite (α), M7 C3 *, MX1(TiX), MX2(VC), MX3((NbTi)C) 400–511
AlN, ferrite (α), M7 C3 *, MX1(TiX), MX2(VC), MX3((NbTi)C), cementite 511–524
AlN, ferrite (α), M7 C3 *, MX1(TiX), MX3((NbTi)C), cementite 524–539
AlN, ferrite (α), MX1(TiX), MX3((NbTi)C), cementite 539–688
AlN, ferrite (α), austenite (γ), MX2(TiX), MX3((NbTi)C), cementite 688–715
AlN, ferrite (α), austenite (γ), MX2(TiX), MX3((NbTi)C) 715–894
AlN, austenite (γ), MX2(TiN), MX3((NbTi)C) 894–957
AlN, austenite (γ), MX2(TiN) 957–1278
AlN, austenite (γ) 1278–1425
austenite (γ) 1425–1480
Liquid, austenite (γ) 1480–1484
Liquid, δ-ferrite, austenite (γ) 1484–1485
Liquid, δ-ferrite 1485–1517
Liquid 1517-
Materials 2022, 14, x FOR PEER REVIEW 10 of 14
* Relating to the chemical composition of the experimental steel, the M7 C3 carbide can be considered to
be Cr-carbide.

Figure 11. Calculated mole fraction of stable phases in the dependence of temperature for the
Figure 11. Calculated mole fraction of stable phases in the dependence of temperature for the
C-Mn-Al HSLA steel using Thermo—Calc software.
C-Mn-Al HSLA steel using Thermo—Calc software.

4.4.Discussion
Discussion
Thiswork
This workisisfocused
focusedon
onfinding
findingthe
the relation
relationbetween
betweenaustenitization
austenitizationtemperature
temperatureand
and
hot ductility
hot ductility of C-Mn-Al
C-Mn-AlHSLA
HSLAsteel.
steel.Hot
Hotductility results
ductility defined
results by the
defined reduction
by the of area
reduction of
for particular test temperatures from 600 °C to ◦
1200 °C are◦ shown in Figure 2. From
area for particular test temperatures from 600 C to 1200 C are shown in Figure 2. From graph-
ical dependences, it is evident that the austenitization temperature influenced the shift of
the temperature range of plasticity drop.
To better explain the causes of the decrease in plasticity, the individual austenitiza-
tion temperatures were divided into main zones. For the austenitization at 1250 °C/30 s,
there are three zones: zone 1 in the temperature range of 1200–1000 °C with plasticity 95–
Materials 2022, 15, 922 11 of 14

graphical dependences, it is evident that the austenitization temperature influenced the

shift of the temperature range of plasticity drop.
To better explain the causes of the decrease in plasticity, the individual austenitization
temperatures were divided into main zones. For the austenitization at 1250 ◦ C/30 s, there
are three zones: zone 1 in the temperature range of 1200–1000 ◦ C with plasticity 95–90%,
zone 2 in the temperature range of 1000–850 ◦ C with a significant decrease in plasticity
from 85% to 45%, and zone 3 in the temperature range of 850–600 ◦ C with an increase in
plasticity from 45% to 75%. For the austenitization at 1350 ◦ C/30 s, there are four zones:
zone 1 in the temperature range of 1200–1100 ◦ C with plasticity 90–85%, zone 2 in the
temperature range of 1100–1000 ◦ C with a significant decrease in plasticity from 85% to
35%, zone 3 in the temperature range of 1000–800 ◦ C with low plasticity from 35% to 30%,
and zone 4 in the temperature range of 800–600 ◦ C with an increase in plasticity from 35%
to 65%.
Plasticity in the temperature range of 1200–1000 ◦ C (which is characterized by zone 1
for both austenitization temperatures) is very sensitive to the amounts of impurities, such
as sulfur and oxygen, in the steel. Thus, the high plasticity values can be attributed to the
favorable Mn/S ratio as well as the small amount of non-coarse precipitates, in particular
AlN, formed at the austenitic grain boundaries [7,18].
The decrease in plasticity in the range of 1100–800 ◦ C, which in this case is charac-
terized by zone 2 at austenitization of 1250 ◦ C/30 s and zones 2 and 3 at austenitization
of 1350 ◦ C/30 s, is often attributed to the unfavorable Mn/S ratio and particular thermal
history of the steel. Steel with Mn/S ratio above 60 is not embrittled, because the sulfur
is tied to the stable phase, MnS, which precipitates in the matrix, not predominantly at
the grain boundaries like FeS. Thermal history is significantly more complex, because it
includes several variables such as melting/freezing in-situ, reheating from room tempera-
ture, cooling rate, isothermal holding temperature, and holding time. Loss of ductility in
this temperature range usually decreases with decreased cooling rate, decreased holding
temperature and increased holding time. Strain rate does not appear to have much effect
on the ductility [7,18,20]. In the steel we studied, a significant decrease in plasticity was
associated with the weakening of the austenitic grain boundaries, which was caused by
coarse precipitates, especially AlN and AlN MnS. This fact was confirmed by the results
of metallographic analyzes performed on samples at a test temperature of 1000 ◦ C (for
both austenitization temperatures), where the largest difference in plasticity was mea-
sured, up to 55%. Analysis of the fracture surfaces (Figures 5 and 6) showed significant
differences in the fracture mechanism. While Sample 1 (austenitization 1250 ◦ C/30 s)
showed significant stretching and formation of the neck, and finally at the center of the
neck the fracture formed, Sample 2 (austenitization 1350 ◦ C/30 s) showed mild stretching
and almost no neck formation, with a small reduction in area. The fracture mechanism
at Sample 1 was the occurrence of dimples, while fracture at Sample 2 was brittle and
intergranular with low energy to break. The reason for the brittle fracture in Sample 2 was
further investigated. As it can be seen in Figures 6 and 9, the coarse precipitates of AlN
and AlN-MnS at the grain boundaries were detected on the fracture surfaces as well as
in the cross-section close to the fracture line. To define the ratio between AlN, AlN-MnS,
and the other particles from the Al+Mn subclass, SEM-based AZtec Feature analysis on an
area of 5 × 5 mm was performed. The analysis results show a significant predominance of
AlN particles in comparison with other found AlN-MnS, AlMgO, AlN-AlO, and AlO in the
ratio 586:203:152:60:2, respectively. As can be seen in Table 2 and Figure 11, the particles
with sizes within 3.01–4.00 µm represents the biggest volume, followed by particles with
size within 2.01–3.00 µm, 4.01–5.00 µm, 5.01–10.00 µm, and 1.00–2.00 µm and greater than
10 µm. Considering several types of research on fracture surfaces, there is clear evidence
that poor hot ductility of investigated steels was associated with the presence of AlN
and/or AlN-MnS particles [10,11,17,25–33]. Precipitation kinetics simulations performed
by the authors of [29] showed that longer holding time leads to growth of AlN at grain
boundaries, a coarsening of MnS at dislocations, and a coarsening and growth of AlN at
Materials 2022, 15, 922 12 of 14

MnS. The authors of [31] found that in FeCrAl steel, the number of AlN particles increases
with increasing cooling rate, although the volume fraction is relatively unaffected. The
authors of [10] found that an increase in Al content from 0.5% to 6% increased the number
of complex MnS inclusions by approx. 4 times. Based on results in Figure 11 and Table 3,
the AlN particles are present in microstructure from 1425 ◦ C to a temperature of 400 ◦ C.
However, the AlN precipitates are stable below 400 ◦ C as well. Based on Thermo-Calc
software results, it can be stated that at a temperature higher than 1200 ◦ C, small AlN
particles dissolve, and thermodynamically more stable particles at grain boundaries grow.
At a temperature higher than 1425 ◦ C AlN, particles dissolve fully in γ-Fe. It can be stated
that experimental results correspond with those calculated using Thermo-Calc software
quite well. The results obtained by the authors of [13] showed that the solubility of AlN
ranged from 1449 ◦ C to 1549 ◦ C in TWIP multi-component Fe-Mn-Si-C-Al steel (24 wt%
Mn, 0.3 wt% Si, 0.6 wt%C, 1.3 wt% Al). Some authors used FactSage software to calculate
the solubility of AlN in various chemical steel concepts [10,17,33]. The authors of [17]
determined that AlN do not precipitate in liquid steel with the composition of 0.12 wt% C,
2.03 wt% Mn, 3 wt% Al, 3 wt% Si, and 0.0004 wt% N or 0.12 wt% C, 5.1 wt% Mn, 2.8 wt%
Al, 3 wt% Si, and 0.0006 wt% N. On the other hand, in steel with a composition of 0.12 wt%
C, 20.6 wt% Mn, 2.8 wt% Al, 3.5 wt% Si, and 0.0011 wt% N, AlN can be formed in liquid
steel during cooling from 1599 ◦ C. The authors of [10] investigated the solubility of AlN
in 7 different chemical concepts of AHSS steels, but none of them corresponded very well
to our C-Mn-Al HSLA steel. For steel with an Al content of 0.9 wt%, the stability of AlN
was determined at 1370 ◦ C. The authors of [33] calculated that in steel with 0.04 wt% C,
0.24 wt% Mn, 3.0 wt% Si, 0.01 wt% Al, and 0.004 wt% O, AlN is formed at the last stage of
solidification, and the condition of its formation is low oxygen content in the steel.
The decrease in plasticity in the temperature range of 850–600 ◦ C, which in this case
is characterized by zone 3 (austenitization of 1250 ◦ C/30 s) and zone 4 (austenitization
of 1350 ◦ C/30 s), is often attributed to a two-phase (austenite-ferrite) region. Controlling
factors for this embrittlement are grain boundary sliding and the localization of strain
to the proeutectoid ferrite film along the austenite grain boundary, which is produced
by the γ→α transformation. Although much research has been done, the embrittlement
mechanism has not been understood completely yet [4–7]. Based on the results of previous
research [34] where the γ→α phase transformation temperatures Ar3 -Ar1 (894–688 ◦ C)
were determined by Thermo-Calc software for C-Mn-Al HSLA steel, it can be believed that
the above-mentioned mechanism was the cause of embrittlement in zone 3 (austenitization
of 1250 ◦ C/30 s) and zone 4 (austenitization of 1350 ◦ C/30 s).
Some studies declare that the critical RA value for surface crack formation during
the continuous casting process is less than 60% [1,25]. Based on these findings, RA less
than 60% was measured in the range of 700–900 ◦ C at austenitization of 1250 ◦ C/30 s and
in range of 630–1080 ◦ C at austenitization of 1350 ◦ C/30 s. Despite a wide range of hot
ductility studies performed for different steel concepts, none of them corresponds very
well to investigated C-Mn-Al HSLA steel chemistry. The results of this research, therefore,
extend knowledge related to hot ductility, especially for HSLA steels.

5. Conclusions
In the present study, the effect of austenitization temperature at 1250 ◦ C and 1350 ◦ C
with 30 s soaking on the hot ductility of C-Mn-Al HSLA steel was studied. Based on results
achieved, the following conclusions can be stated:
• For the test temperature of 1200 ◦ C, maximum plasticity of 90% and 85% for austen-
itization temperatures 1250 ◦ C/30 s and 1350 ◦ C/30 s, respectively, was measured.
Minimum plasticity of 45% for test temperature of 850 ◦ C and 30% for test temper-
atures from 850 ◦ C to 950 ◦ C and austenitization temperatures of 1250 ◦ C/30 s and
1350 ◦ C/30 s, respectively, was determined.
Materials 2022, 15, 922 13 of 14

• While the sample after austenitization at 1250 ◦ C/30 s showed a ductile fracture, the
sample after austenitization at 1350 ◦ C/30 s showed a small reduction of area, with
low-energy brittle intergranular fracture.
• AlN and AlN-MnS coarse precipitates at austenite grain boundaries are supposed to
be the reason for brittle intergranular fracturing.
• Using Thermo-Calc software, it was found that AlN particles precipitate from solid
solution below the temperature of 1425 ◦ C.

Author Contributions: Writing—original draft preparation, P.P.; writing—review and editing, T.K.,
J.B., P.Z. (Pavol Zahumensky), V.H., L.J., P.Z. (Pavol Zubko), P.Z. (Peter Zimovcak), R.G. and I.D.;
investigation, P.P., T.K., J.B., P.Z. (Pavol Zahumensky), V.H., L.J., P.Z. (Pavol Zubko), P.Z. (Peter
Zimovcak), R.G. and I.D.; supervision, T.K. and J.B.; methodology, P.P., T.K., J.B., P.Z. (Pavol Zahu-
mensky), V.H. and P.Z. (Pavol Zubko); validation, T.K. and J.B. critically reviewed the manuscript
and approved its final submitted version. All authors have read and agreed to the published version
of the manuscript.
Funding: This research was supported by VEGA, grant number 1/0599/18.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data sharing is not applicable to this article.
Acknowledgments: The authors would like to thank the U. S. Steel Kosice for permission to publish
this manuscript.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Arıkan, M.M. Hot Ductility Behavior of a Peritectic Steel during Continuous Casting. Metals 2015, 5, 986–999. [CrossRef]
2. Crowther, D.N.; Mintz, B. Influence of carbon on hot ductility of steels. Mater. Sci. Technol. 1986, 2, 671–676. [CrossRef]
3. Chimani, C.M.; Resch, H.; Mörwald, K.; Kolednik, O. Precipitation and phase transformation modelling to predict surface cracks
and slab quality. Ironmak. Steelmak. 2005, 32, 75–79. [CrossRef]
4. Kvackaj, T.; Bidulská, J.; Bidulský, R. Overview of HSS Steel Grades Development and Study of Reheating Condition Effects on
Austenite Grain Size Changes. Materials 2021, 14, 1988. [CrossRef] [PubMed]
5. Kvačkaj, T.; Bacsó, J.; Bidulská, J.; Lupták, M.; Pokorný, I.; Kvačkaj, M.; Vlado, M. Influence of cryo and classic rolling conditions
on proccesing parameters of C-Si steel. Acta Metall. Slovaca 2010, 16, 268–276.
6. Oktay, S.; Şeşen, M.K.; Di Nunzio, P.E. Investigation of the effect of isothermal heat treatments on mechanical properties of
thermo-mechanically rolled S700MC steel grade. Acta Metall. Slovaca 2020, 26, 11–16. [CrossRef]
7. Suzuki, H.G.; Nishimura, S.; Yamaguchi, S. Characteristics of Hot Ductility in Steels Subjected to the Melting and Solidification.
Trans. Iron Steel Inst. Jpn. 1982, 22, 48–56. [CrossRef]
8. Brimacombe, J.K.; Sorimachi, K. Crack formation in the continuous casting of steel. Metall. Trans. B 1977, 8, 489–505. [CrossRef]
9. Paek, M.K.; Jang, J.M.; Do, K.H.; Pak, J.J. Nitrogen solubility in high manganese-aluminum alloyed liquid steels. Met. Mater. Int.
2013, 19, 1077–1081. [CrossRef]
10. Nabeel, M.; Alba, M.; Dogan, N. Influence of Al and N Content and Cooling Rate on the Characteristics of Complex MnS
Inclusions in AHSS. Crystals 2020, 10, 1054. [CrossRef]
11. Penna, R.V.; Bartlett, L.N.; Constance, T. Understanding the Role of Inclusions on the Dynamic Fracture Toughness of High
Strength Lightweight FeMnAl Steels. Int. J. Met. 2019, 13, 286–299. [CrossRef]
12. Némethová, L.; Kvačkaj, T.; Mišičko, R.; Pokorný, I.; Kovárová, I. Structural changes of C-Mn-Nb-V steel during the reheating.
Acta Metall. Slovaca 2009, 3, 173–179.
13. Jang, J.M.; Paek, M.K.; Pak, J.J. Thermodynamics of Nitrogen Solubility and AlN Formation in Multi-Component High Mn Steel
Melts. ISIJ Int. 2017, 57, 1821–1830. [CrossRef]
14. Radis, R.; Kozeschnik, E. Kinetics of AlN precipitation in microalloyed steel. Model. Simul. Mater. Sci. Eng. 2010,
18, 055003. [CrossRef]
15. Bott, J.H.; Yin, H.; Sridhar, S. AlN Formation in High Aluminium Content Fe-Al Alloys. In Proceedings of the 5th International
Congress on the Science and Technology of Steelmaking, Dresden, Germany, 1–3 October 2012.
16. Paek, M.K.; Jang, J.M.; Jiang, M.; Pak, J.J. Thermodynamics of AlN Formation in High Manganese-Aluminum Alloyed Liquid
Steels. ISIJ Int. 2013, 53, 973–978. [CrossRef]
17. Alba, M.; Nabeel, M.; Dogan, N. Investigation of Inclusion Formation in Light-Weight Fe–Mn–Al Steels using Automated
Scanning Electron Microscope Equipped with Energy-Dispersive X-ray Spectroscopy. Steel Res. Int. 2019, 91, 1900477. [CrossRef]
Materials 2022, 15, 922 14 of 14

18. Nachtrab, W.T.; Chou, Y.T. High temperature ductility loss in carbon-manganese and niobium-treated steels. Metall. Mater. Trans.
1986, 17, 1995–2006. [CrossRef]
19. Mintz, B.; Crowther, D.N. Hot ductility of steels and its relationship to the problem of transverse cracking in continuous casting.
Int. Mater. Rev. 2010, 55, 168–196. [CrossRef]
20. Comineli, O.; Abushosha, R.; Mintz, B. Influence of titanium and nitrogen on hot ductility of C–Mn–Nb–Al steels. Mater. Sci.
Technol. 1999, 15, 1058–1068. [CrossRef]
21. Abushosha, R.; Comineli, O.; Mintz, B. Influence of Ti on hot ductility of C–Mn–Al steels. Mater. Sci. Technol. 1999,
15, 278–286. [CrossRef]
22. Mintz, B.; Arrowsmith, J.M. Hot-ductility behaviour of C–Mn–Nb–Al steels and its relationship to crack propagation during the
straightening of continuously cast strand. Met. Technol. 1979, 6, 24–32. [CrossRef]
23. Thomas, B.G.; Samarasekera, I.V.; Brimacombe, J.K. Mathematical model of the thermal processing of steel ingots: Part I. Heat
flow model. Metall. Trans. B 1987, 18, 119–130. [CrossRef]
24. Thermo-Calc Software. Available online: https://thermocalc.com (accessed on 20 November 2021).
25. Yu, Y.C.; Chen, W.Q.; Zheng, H.G. Effects of Ti–Ce Refiners on Solidification Structure and Hot Ductility of Fe–36Ni Invar Alloy. J.
Rare Earths 2013, 31, 927–932. [CrossRef]
26. Li, Q.; Liu, W. Effect of Boron on Hot Ductility and Room Temperature Tensile Properties of Microalloyed Steels with Titanium
and Niobium. Materials 2019, 12, 2290. [CrossRef]
27. Guo, Y.; Zhao, Y.; Song, S. Highly Enhanced Hot Ductility Performance of Advanced SA508-4N RPV Steel by Trace Impurity
Phosphorus and Rare Earth Cerium. Metals 2020, 10, 1598. [CrossRef]
28. He, C.H.; Wang, J.; Chen, Y.; Yu, W.; Tang, D. Effects of Sn and Sb on the Hot Ductility of Nb+Ti Microalloyed Steels. Metals 2020,
10, 1679. [CrossRef]
29. Gontijo, M.; Hoflehner, C.H.; Ilie, S.; Six, J.; Sommitsch, C.H. Holding Time Influence on the Hot Ductility Behavior of a
Continuously Cast Low Alloy Steel. Metals 2021, 11, 64. [CrossRef]
30. Vedani, M.; Ripamonti, D.; Mannucci, A.; Dellasega, D. Hot Ductility of Microalloyed Steels. Metall. Ital. 2008, 100, 19–24.
31. Deng, Z.; He, Y.; Liu, J.; Yan, B.; Yang, Y.; McLean, A. Effect of Cooling Rate on AlN Precipitation in FeCrAl Stainless Steel During
Solidification. Metals 2019, 9, 1091. [CrossRef]
32. Alcantara, F.L.; Barbosa, R.A.N.M.; Cunha, M.A. Aluminium Nitride Precipitation in Fe-3%Si Steel. ISIJ Int. 2013,
53, 1211–1214. [CrossRef]
33. Kalisz, D.; Rzadkosz, S. Modeling of the Formation of AlN Precipitates during Solidification of Steel. Arch. Foundry Eng. 2013, 13,
63–68. [CrossRef]
34. Prislupčák, P.; Kvačkaj, T.; Bidulská, J.; Záhumenský, P.; Homolová, V.; Zimovčák, P. Austenite-Ferrite Transformation Tempera-
tures of C Mn Al HSLA Steel. Acta Metall. Slovaca 2021, 27, 207–209. [CrossRef]