Materials Characterization 194 (2022) 112367

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Materials Characterization
journal homepage: www.elsevier.com/locate/matchar

Characterization of precipitation, evolution, and growth of MnS inclusions

in medium/high manganese steel during solidification process
Jianhua Chu a, Liqiang Zhang a, *, Jian Yang a, Yanping Bao b, Naqash Ali c, Chaojie Zhang a
a
School of Metallurgical Engineering, Anhui University of Technology, Maanshan, 243002, Anhui Province, PR China
b
State Key Lab of Advanced Metallurgy, University of Science & Technology Beijing, Beijing 100083, PR China
c
School of Materials Science and Engineering, Anhui University of Technology, Maanshan, 243002, Anhui Province, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: MnS as a main manganese-containing inclusion in medium/high manganese steel, which can be determined to
Medium/high manganese steel the mechanical properties of steel. However, the precipitation and evolution mechanism of MnS in medium/high
MnS inclusions manganese steel is still unclear due to the special solidification properties and element segregation behavior.
Precipitation behavior
Hence, the effects of sulfur content, manganese content and cooling rate on the precipitation, evolution, and
Solidification
Evolution mechanism
growth behavior of MnS inclusions in medium/high manganese are various experimentally characterized and
thermodynamically elucidated in the present work. The results of 2D and 3D observation indicated that the
morphology of MnS in medium manganese steel were transformed from globular and spindle-like (type I MnS)
into large-sized rods (type II MnS) and dendritic (type D MnS), when sulfur content was increased from 78 ppm
to 1578 ppm. Particularly, the spatial distribution and structure of MnS inclusions are elaborated in detail
through X-ray micro-CT observations, which are discussed by defining the quantitative topography parameters
and statistical analysis. Based on in situ CSLM observations, MnS precipitation path in high sulfur medium
manganese steel was monitored as L → (L + δ + MnS) → (δ + MnS) → (δ + γ + MnS) → (γ + MnS) → (α + γ +
MnS) → (α+MnS). Simultaneously, the Scheil-solidification calculations demonstrated that MnS is precipitated at
the interdendritic region where the solid-liquid states are coexisted, which is caused by the segregation of sulfur
and manganese. Moreover, increasing sulfur content generates the earlier precipitation, and leads to the sig­
nificant increase in the number and size of MnS inclusions. Besides, the increase of manganese content promotes
the transition of MnS from globular to polyhedral shape, which is attributed to the dissociative eutectic reaction
of MnS formation preferentially takes place earlier in case of high manganese steel. It is also found that the
decreasing of cooling rate and increasing the manganese content tends to increase the number and size of MnS
inclusions, which is resulted from the long growth times of high manganese steel induced by large solid-liquid
temperature differences. This work provides a systematic understanding of the precipitation and evolution of
MnS inclusions in medium/high manganese steel.

1. Introduction
Currently, advanced high-strength steels (AHSS) have been captured
extensively attention in the automotive industry, which is result from
the growing demands for the lightweight body with higher strength
pursued exhaust emission reduction, fuel economy and vehicle safety
[1–4]. Encouragingly, medium manganese and high manganese
transformation-induced-plasticity (TRIP)/twinning-induced-plasticity
(TWIP) steel have been developed, which are the most promising can­
didates for the next-generation of AHSS, owing to their excellent balance
of high strain hardening, strength and energy absorption, superior
toughness and good ductility [5–7]. In this context, the optimized
chemical composition design, strengthening mechanism, microstructure
evolution control, in-service functional properties and heat treatment
processes have been extensively investigated over the last decade to
achieve the desired mechanical properties [8–11]. It is well considered
that the mechanical properties and hot-working behavior depend on the
non-metallic inclusions behavior [12,13], while the effect of inclusions
on the physicochemical properties of medium and high manganese
steels has also been noted recently.
Park et al. [14] reported that the inclusions in Fe-Mn-Al high man­
ganese steels can be classified into seven types, including Al2O3, AlN or

* Corresponding author.
E-mail address: zhangsir508@163.com (L. Zhang).

https://doi.org/10.1016/j.matchar.2022.112367
Received 4 August 2022; Received in revised form 17 September 2022; Accepted 1 October 2022
Available online 6 October 2022
1044-5803/© 2022 Elsevier Inc. All rights reserved.
J. Chu et al.
Fig. 1. (a) Schematic diagram of vertical tube furnace and (b) heating curve and cooling methodology.
AlON, MnAl2O4, Al2O3(-Al(O)N), Mn(S,Se), Al2O3-Mn(S,Se), Al2O3(-Al
(O)N)-Mn(S,Se), and it is showed that the volume fraction of inclusions
is the largest when the Al content reaches 3%. Xin et al. [15] revealed
that the dominant sulphide inclusion in Fe–16Mn–xAl–0.6C high man­
ganese TWIP steels followed the route of MnO → Al2O3/MnS → MnS →
AlN when Al content was increased from 0.002 to 2.1%. Inclusion
characteristics in medium manganese Fe–5Mn–xAl steels [16] indicated
that the total amount of inclusions was increased significantly with
increasing Al content, and MnS was preferably co-precipitated with AlN
at grain boundaries during solidification. Besides, Wang et al. [17] re­
ported the effect of cooling conditions on the inclusions evolution in
high manganese TWIP steels, and discussed the deteriorate mechanism
of AlN to hot ductility. It can be found that the numerous studies focused
on the effect of Al content on the evolution of inclusions and mechanical
properties of medium/high manganese steel. However, MnS inclusions
as the main manganese-containing inclusion in medium/high manga­
nese steel, which is attributed to the inevitable contamination by S or Se
impurity from alloy raw material and the actual production processes
[14].
The MnS inclusions were proved to elongate easily during the hot-
working of steel due to its special characteristics of high deformation
and similar thermal expansion coefficient to the steel matrix, resulting in
the deterioration of plasticity and the fracture toughness of the steel was
suffered from the formation of flaws [18,19]. Furthermore, the large
MnS inclusion precipitation at grain boundaries induces the stress con­
tent, accelerates the grain boundary slip and decreases the crack resis­
tance [20]. On the other hand, soft and globular MnS particles act as
nucleation of intra-granular ferrites [21], promote precipitation around
the oxide and nitride inclusions, and have detrimental effect of in­
clusions reduction [22], which improves the machinability of steel due
to low power requirement for shear [23,24]. Therefore, mechanical
properties of steels can be significantly controlled by the morphology,
types, size, and distribution of MnS inclusions [25,26], and it is crucial
to clarify the characteristics and formation mechanism of MnS. Lin et al.
evaluated the different types of reactions for the formation of MnS
during solidification of free-cutting steels based on CALPHAD thermo­
dynamic modelling, and found that the MnS morphology can be
controlled by the solidification path [27]. From this perspective, the
solidification characteristics and segregation behavior of manganese
Table 1
Composition of the IF steel sample and manganese metal block.
Compositon [C] [Si] [Mn] [P]
IF steel 0.004 0.005 0.137 0.017
Mn block 0.05 0.3 99 0.03
2
Materials Characterization 194 (2022) 112367
and sulfur in medium/high manganese steels were significantly different
from the conventional steels [19,28], thus the precipitation and growth
behavior of MnS are essential to be further revealed. Unfortunately, the
comprehensive analysis and characterization on precipitation behavior
of MnS inclusions in medium/high manganese steel steels have been
rarely reported, and corresponding formation and evolution mecha­
nisms are still unclear.
Hence, in this paper, the effects of sulfur content, manganese con­
tent, and cooling rates on amount, size, composition, along with 2D and
3D morphology of MnS inclusions in medium/high manganese steel are
systematically investigated by various experimental techniques, and the
corresponding microsegregation behavior based on Scheil-solidification
calculations is discussed by using thermo-calc software. Furthermore,
the precipitation and evolution mechanism of MnS in medium/high
manganese steels are revealed, and the precipitation process of MnS in
different phases during solidification was confirmed by in situ obser­
vation experiments. Moreover, an advanced micro-CT detection tech­
nology was employed for evaluating the 3D morphology parameter and
spatial distribution of different types of MnS in high‑sulfur medi­
um‑manganese steels. Besides, the growth behaviors of MnS inclusions
under different cooling rates were also analyzed with the help of elec­
tron probe microanalysis and Raman spectrum. This work provides an
effectual basis for the control of MnS inclusions in industrial
manufacturing of high-quality medium/high manganese steels.
2. Experiment
2.1. Experimental procedure
To investigate the MnS inclusion behaviors of medium/high man­
ganese steel, the laboratory experiments were carried out by employing
a vertical tubular resistance furnace (SKL16–8, Baotou, P.R. China), as
shown in Fig. 1 a. IF steel samples were provided from a steel plant,
while the manganese metal blocks and FeS chemical reagent (AR ≥
99%) were used to prepare the steel sample with different manganese
and sulfur content, and corresponding chemical compositions are listed
in Table 1. Prior to the experiments, the IF steel was cut into square
columns with rough weight of 400 g, and were put into a corundum
crucible (inner diameter, 60 mm; outer diameter, 68 mm; height, 120
[S] [Al] [Ti] T. O [N]
0.009 0.036 0.056 0.002 0.003
0.02 – – 0.03 0.01
J. Chu et al. Materials Characterization 194 (2022) 112367

Fig. 2. Experimental scheme of MnS precipitation in manganese steel with different (a) sulfur and (b) manganese contents and (c) sample analysis method.

manganese is higher and the melting time is longer, so that the longer
Table 2
time interval for sample M3 and M4. Ultimately, these metal samples
Chemical composition of manganese steel with different sulfur and manganese
were prepared for chemical analysis as shown in Fig. 2c. Inductively
content, wt%.
coupled plasma-atomic emission spectrometry (PerkinElmer Analyst
Samples [Mn] [C] [S] Samples [Mn] [C] [S]
ICP-OES 8300) and direct reading spectrometer were employed to
S0 4.52 0.0862 0.0078 M0 0.24 0.017 0.0224 determine the contents of manganese and aluminum, while the carbon
S1 4.49 0.0593 0.0312 M1 2.09 0.049 0.0207 and sulfur contents were detected by carbon and sulfur analyzer, and the
S2 4.54 0.0486 0.0618 M2 6.22 0.049 0.0205
S3 4.57 0.0480 0.1153 M3 13.26 0.053 0.0202
measured chemical compositions of samples are listed in Table 2.
S4 4.51 0.0419 0.1578 M4 32.93 0.063 0.0193

2.2. Characterization of MnS inclusions

mm) which was protected by a larger graphite crucible, then located in
constant temperature zone of corundum tube under an argon (99%
purity) protective atmosphere. Fig. 1 b shows the temperature profile
measured by B-type thermocouple by using Si–Mo bar heating.
The master materials (IF steel) were heated at 1600 ◦ C for 10 min to
obtain the molten steel. A certain amount of aluminum shots was
dropped into the molten pool through the quartz tube to deoxidize the
molten steel, and followed by the manganese blocks wrapped in tin foil
were added after 2 min to achieve the targeted manganese content of
4.5% as shown in Fig. 2a. The system was then equilibrated for 30 min,
the first steel sample was taken quickly by a long rod pail sampler and
quenched in a water-cooled container, and then the FeS packed in a tin
foil was added immediately. In subsequent experiments, the steel sam­
ples with different sulfur content were collected at the time interval of
20 min after FeS addition, then followed by water quenching, which was
defined as the S0, S1, S2, S3, S4, respectively. After S4 sample was taken
out, the remaining three samples were air-cooled (AC) and remelted in
the furnace at the cooling rate of 5 ◦ C/min (FC-5) and 20 ◦ C/min (FC-
20), respectively (Fig. 1b). Therefore, the S4 is named water-cooled
sample (WC), whose chemical composition is consistent with FC-5, FC-
20 and AC samples. Similarly, the several water quenched samples
named as M0, M1, M2, M3 and M4 were obtained to observe the pre­
cipitation behavior of MnS in steel ([S] ≈ 200 ppm) with different
manganese content as depicted in Fig. 2b. In order to achieve higher
manganese content in subsequent samples, the quality of the prepared
Fig. 2c illustrates the MnS inclusions analysis methods of the steel
sample. The 10 mm × 10 mm × 10 mm cubic metallographic samples
were prepared from the central position of steel sample, then mirror
polished for 2D morphology and chemical composition analysis of MnS
inclusion by using scanning electron microscope equipped with energy-
dispersive spectrometry (SEM-EDS, PhenomProX, Holland). The size,
area, and number of MnS inclusions with larger than 1 μm was statis­
tically analyzed by the ASPEX inclusion automatic analysis system. In
order to achieve an accurate composition of inclusions, the electron
probe microanalysis (EPMA) was implemented over the total exposed
area of each inclusion. Subsequently, 3D morphology of MnS was
observed by surface electrolysis of metallographic samples in AA solu­
tion (89% methanol, 1% tetra methyl ammonium chloride and 10%
acetyl acetone to a total volume of 250 mL), and the SEM detection with
EDS analysis also was used to characterization.
Furthermore, the high-temperature confocal laser scanning micro­
scope (CLSM) was used to in situ observe the precipitation process of
MnS during the solidification of molten steel. The sample were cut into
small cylindrical specimens with the size of Φ3 × 4 mm and carefully
polished, then it was put into a corundum crucible which was placed in
the sample holder in the CLSM furnace. The small cylindrical specimens
were rapidly heated (200 ◦ C/min) up to 1550 ◦ C and held for 5 min,
after that these were cooled (100 ◦ C/min) until 1000 ◦ C under argon
atmosphere. The MnS precipitation upon solidification was captured
with real-time focus at a picture per second with 1024 × 1024-pixel

3
J. Chu et al.
Fig. 3. (a-m) 2D morphologies and distribution of MnS in medium manganese steels with different sulfur contents. (n) The number density and (o) areal density of
MnS-type inclusions in manganese steel with different sulfur contents.
resolution. Moreover, the detailed 3D structural features of MnS in­
clusions were non-destructively elucidated by using X-ray micro-CT,
which performed the reconstruction of 2D cross-sectional images and
3D objects on a tomography imaging system (Xradia 510 Versa) via
secondary imaging magnification technology. The samples were pro­
cessed into needle-shape with a diameter approximately 1 mm, resulting
difference in the X-ray linear attenuation coefficients (LAC) between Fe
matrix and MnS >10% with high spatial resolution [29]. The observa­
tion field of the detector was 1 mm × 1 mm with a 2D output resolution
of 2048 × 2048 in pixels via XM3DViewer and ORS software, which
yielded a pixel size of 0.9 μm.
3. Results
3.1. Two-dimensional characteristics of MnS in medium manganese steel
with different sulfur content
The typical 2D morphologies of MnS inclusions were observed in
samples with different sulfur content are shown in Fig. 3. The MnS in­
clusions in S0 sample (Fig. 3a, b) and S1 sample (Fig. 3c, d) have been
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Materials Characterization 194 (2022) 112367
appeared as a single globular or spindle shape particles. With the in­
crease of sulfur content, it is obvious that MnS particles tends to
aggregate and precipitate along the grain boundary (Fig. 3e-h). When
the sulfur content increased up to 1578 ppm (S4 sample), two categories
of MnS inclusions including the fine particles and long strips shape were
detected as shown in Fig. 3i-j, which is further confirmed by the element
mapping analysis as shown in Fig. 3 k-m, and verifies the formation of
MnS. To quantitatively investigate the effect of sulfur content on the size
and number of MnS inclusions, a statistical characterize was conducted
in this study. When sulfur content was increased from 78 ppm to 1578
ppm, the corresponding number density of MnS inclusions was signifi­
cantly increased from 22.57 per mm2 to 496.27 per mm2 as shown in
Fig. 3n. Similarly, the areal density of MnS inclusions was increased
from 157.66 μm2/mm2 to 62.133 μm2/mm2 (Fig. 3o), which means that
the excessive content of sulfur causes a large number of MnS inclusions
formation.
To further clarify the precipitation process of MnS in more detail, the
S4 sample was observed by high-temperature confocal microscopy. As
shown in Fig. 4a, the liquidus temperature of the present medium
manganese steel is 1535.2 ◦ C. This temperature is deviated from the
J. Chu et al.
Fig. 4. In-situ precipitation process of phase and MnS in S4 sample.
thermodynamic calculations results and can be attributed to the location
of thermocouple below the test crucible which slightly lowers the tem­
perature. When the temperature was decreased to 1524.8 ◦ C, the pri­
mary δ-Fe phase was occurred on the surface of the molten pool, as
shown in Fig. 4b [30]. The black dotted MnS inclusions near the δ-Fe
grains were precipitated at the δ/L interface when temperature was
decreased to 1518.2 ◦ C (Fig. 4c), which was indicated by a red circle.
The more δ-Fe grains were formed and continued to grow with the
decrease of temperature, and emerged as the grains boundaries of the
δ-Fe (Fig. 4d, e). Until the temperature decreases to 1505.7 ◦ C as shown
in Fig. 4f, a thin layer of the γ-Fe phase generated the δ grain boundary,
which is a typical sign of ferrite to austenite transformation at high
temperature. The liquid phase is disappeared at 1495.6 ◦ C as shown in
Fig. 7g, which is mainly transformed into the δ-Fe and γ-Fe phases.
Subsequently, the emerging δ/γ interface is propagated and expanded
toward the multiple directions with the further decrease of temperature
(Fig. 4g-i), as a result the δ-Fe grains tend to coarsen and reduce
continuously [28]. Simultaneously, MnS precipitation was dominant
around the grain boundary when the temperature was decreased.
3.2. Three-dimensional characteristics of MnS in medium manganese steel
with different sulfur content
Furthermore, Fig. 5 shows the 3D morphologies of MnS inclusions in
medium manganese steel. Single-particle MnS with granular or spindle
shape were also found in S0 sample (Fig. 5a, b). The rod and dendritic-
like morphologies of MnS in S1 sample with a slightly larger size, while
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Materials Characterization 194 (2022) 112367
the granular MnS is also evident which can be seen in Fig. 5c, d. In
particular, Fig. 5e, f shows that the clusters of MnS contain the free as­
sembly of rods, which are mainly connected with each other in S2
sample. Moreover, a large number of small particles and clusters of MnS
were also precipitated between the dendrites in case of S3 and S4
samples (Fig. 5 g-l), while the size and precipitation amount were
increased significantly, which can be attributed the high sulfur content
provides a large number of nucleation sites for MnS precipitation.
Overall, it was found that the morphology of MnS was transformed from
globular and spindle-like (type I MnS) into large-sized rods (type II MnS)
and dendritic (type D MnS) [31], and finally into clustered MnS with the
increase of sulfur content.
The inclusions are conventionally not fully exposed or eroded by the
inclusion electrolysis method. X-ray micro-CT as a nondestructive
detection technique exposes the statistics of accurate 3D morphology,
size, and special distribution of MnS inclusions in detail, as the con­
ventional 2D characterization by using optical microscopy (OM) and
(SEM) cannot reveal the actual 3D morphology of MnS inclusions.
Fig. 6a shows the principle of X-ray micro-CT. The parallel X-ray beam
from energy source penetrates the sample and through the secondary
amplification of scintillator and proprietary optics, rendering a 2D
image in charge coupled device (CCD) detector by absorbing the
contrast of the sample [32]. On the other hand, the multiple radiograph
projection images at different angles were collected by rotation of the
sample, generating a 3D reconstructed image. Specifically, Fig. 6b shows
representative 3D spatial distribution renderings of the MnS inclusions
within the gauge cylinder volume of 1mm3 for the S4 samples. It is found
J. Chu et al. Materials Characterization 194 (2022) 112367

Fig. 5. (a-l) 3D morphologies of MnS in medium manganese steels with different sulfur contents.

Fig. 6. (a) The working principle of high-resolution micro-CT based on secondary magnification technology. (b) 3D morphologies and related parameters of different
MnS inclusions in S4 sample.

6
 J. Chu et al.
7

Materials Characterization 194 (2022) 112367

Fig. 7. The distribution and number frequency of (a, b) aspect ratio, (c, d) mean ferret diameter and (e, f) Phi of MnS inclusions in S4 sample.
J. Chu et al.
Fig. 8. (a-j) 3D morphologies and (k-l) quantitative analysis of MnS inclusions in steels with different manganese contents.
that about 1056 particles of MnS inclusions are unevenly distributed in
the 3D space, which mainly appeared as the majority of globular,
spindle-like, rod-like particles and cluster-like particles with a larger
size, which is consistent with the surface electrolysis results. Moreover,
the colors of MnS particles in the figures are distinguished individually
in the 3D space volume, and the volume ranges are increased from 1.83
μm3 to 61,540.44 μm3.
Furthermore, to quantitatively evaluate the 3D size and structure of
MnS inclusions, a series of morphological characteristics parameters are
used to define the four typical single MnS inclusion particles, which are
extracted from the 3D space as shown in Fig. 7a. Accordingly, the
equivalent spherical diameters (Deq) and the shape factor (φ) can be
investigated to quantify the size and shape of MnS inclusion, which is
calculated by the following equations respectively [33,34]:.
√̅̅̅̅̅̅
3 6V
Deq =
π
S3
φ=
36πV 2
where V and S is the volume and surface area of MnS particle, respec­
tively. The shape factor closer to 1 exhibits the spherical shape of in­
clusions [29]. The shape factor for globular inclusions reaches to 1.28,
3– 5 for irregular ellipsoid and rod-shaped MnS, while the shape factor
becomes much larger than 150 as the clustered MnS is consisted on
globular and rod particles, showing that the inclusions contain the
complicated shapes. Besides, the 3D feret diameter was also employed to
assess the size of an inclusion particle, which is defined as the largest
distance between two parallel lines touching the particle without
intersecting it [33]. It can be seen that the equivalent diameter is 12.78–
48.33 μm, maximum feret diameter is 15.92– 273.54 μm, average feret
diameter is 13.96– 214.49 μm, and the size of the clustered MnS is the
8
Materials Characterization 194 (2022) 112367
largest among them. Fig. 7b, d, f shows the statistical distribution of the
number frequency and accumulative number frequency for aspect ratio,
mean feret diameter and angle in the horizontal plane for the MnS in­
clusions in the samples, while the corresponding 3D distributions and
color map are shown in Fig. 7a, c, e, respectively. It is evident that
93.74% of the inclusions have an aspect ratio <0.7, which indicates that
the MnS inclusions have aspherical shape (Fig. 7b). As was expected, the
peaks of the mean feret diameter of MnS particles is <10 μm, and the
proportion of MnS with a mean feret diameter smaller than 40 μm is
>95% (Fig. 7d), which is attributed to the formation of a large number
of fine MnS particles. In addition, the cumulative frequency of angle in
the horizontal plane for MnS inclusions is also increased (Fig. 7f), which
suggests that the distribution direction of inclusion is relatively uniform.
3.3. Characteristics of MnS in steel with different manganese content
Fig. 8 a-j represents the typical 3D morphology of inclusions in steel
samples with different manganese contents. The globular and spindle-
shaped MnS is observed in the investigated steel with 0.24% manga­
nese content, and their size is <5 μm (Fig. 8a). For the M1, M2, and M3
samples, the corresponding manganese content increases from 2.09 to
13.26% (Fig. 8b-g), and the precipitated MnS appear with various
shapes, including globular, rod, and irregular dendritic with sizes >20
μm, and also the number of MnS is increased significantly. Particularly,
it is clearly observed that the great amount of polyhedral shape MnS
(type III) with manganese content of 32.93% (Fig. 8 h-j), suggests that
the increase of manganese content can promote the transformation into
type III MnS. Moreover, the number density of MnS inclusions is
increased from 6.21 per mm2 to 69.25 per mm2 (Fig. 8 k) with the in­
crease of manganese content from 0.24% to 32.93%, and the corre­
sponding areal density is increased from 10.51 to 111.23 μm2⋅mm− 2
(Fig. 8 l).
J. Chu et al.
Fig. 9. The EPMA images of (a-c) AC and (d-f) FC-5 samples and (g-n) the 3D morphologies of MnS with different cooling rate.
3.4. Characteristics of MnS in medium manganese steel with different
cooling rate
The 2D morphologies and chemical compositions of MnS inclusions
for AC and FC-5 samples were detected by EPMA (SEM-WDS) analysis,
which is shown in Fig. 9a-f. It can be clearly seen that the air cooled
samples have granular MnS, while the rod-shaped MnS with large size is
appeared in the furnace cooled samples. The distribution of manganese
and sulfur elements are almost overlapping, which clearly confirms the
sulphide phase. Fig. 9g-n shows 3D morphologies of MnS in manganese
steel at different cooling rates. As illustrated in Fig. 9g-l, not only exhibit
a large number of globular and rod-shaped MnS, but the array-shaped
MnS clusters with size of about 100 μm can also be observed. The size
of MnS in the air cooled sample is approximately 20 μm (Fig. 9m, n), and
it is also composed of rod.
Moreover, the Raman characterization of the globular-shaped and
strip-shaped MnS in the FC-5 sample was also investigated. As shown in
Fig. 10a, the peaks are located at 186, 222, 321 and 585 cm− 1, which are
attributed to the α-(Fe, Mn)S transverse optical phonon and longitudinal
optical phonon vibrational modes [35,36], and confirms the same type
of α-MnS phase. Additionly, the sizes of the MnS inclusions in high sulfur
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Materials Characterization 194 (2022) 112367
steel samples is concentrated 1–2 μm (Fig. 10b), which are mainly
caused by the precipitation of a large number MnS particles. Overall, the
size of MnS inclusions increases with the decrease of cooling rate,
especially the proportion of inclusions larger than 4 μm was increased
significantly. Fig. 10 c, d shows that, the number density of MnS in­
clusions is increased from 146.38 per mm2 to 495.91⋅per mm2, and the
areal density is increased from 195.86 μm2⋅mm− 2 to 621.33 μm2⋅mm− 2
when the cooling method is transformed from slow furnace cooling of
5 ◦ C⋅min− 1 to water cooling.
4. Discussions
4.1. The precipitation and evolution mechanism of MnS in medium
manganese steel with different sulfur content
Based on aforementioned in situ observation of MnS precipitation
results (Fig. 4) by high-temperature confocal microscopy experiment,
and combined with the equilibrium precipitation phase diagram of Fe-
MnS (Fig. 11 a-b), the diagram of the precipitation process of MnS
with different phase transitions as shown in Fig. 11 c. At first, the MnS
particle nucleates and grows at the boundaries of primary dendritic δ-Fe
J. Chu et al.
Fig. 10. (a) Raman spectra of MnS with different morphologies in the FC-5 sample, (b) the number ratio, (c) number density and (d) areal density of MnS-type
inclusions in manganese steels with different cooling rate.
phase in high sulfur medium manganese steel. The MnS inclusions
gradually separates from the δ-Fe phase into the γ-Fe phase accompa­
nied with the phase transition during the solidification process, which
leads to the formation of α-Fe + MnS phase at room temperature.
Consequently, the MnS precipitation of the experimental steel follows
the route as: L → (L + δ + MnS) → (δ + MnS) → (δ + γ + MnS) → (γ +
MnS) → (α + γ + MnS) → (α + MnS).
Precipitation of inclusions takes place when the actual content of
product becomes greater than the equilibrium content of product.
During the solidification process, the solute elements of manganese and
sulfur are redistributed between the solid and liquid phases due to
micro-segregation of elements, which restricts the precipitation and
growth behavior of MnS inclusions. Therefore, the segregation behavior
of manganese and sulfur contents is evaluated by the non-equilibrium
solidification process of medium manganese steel samples with
different sulfur contents, which is simulated by the Scheil-Gulliver
module by using the commercial Thermo-Calc software. It is found
that the solid and liquid phase temperature of medium manganese steel
with slight change along with the increase of sulfur content (inset of
Fig. 12a). The variation of manganese and sulfur content in liquid steel
with solid fraction were calculated in Fig. 5a, b. It is clearly evident that
the content of both manganese and sulfur increased initially as the so­
lidification progressed and they were also tending to segregate contin­
uously, but an obvious inflection point was occurred at sulfur content
curve (Fig. 12b), while manganese content continued to increase rapidly
up to the end of solidification. It should be noted that the inflection point
is considered as the starting time for the MnS precipitation, which
consumed a certain amount of manganese and sulfur, as a result their
content were decreased [20]. Even so, initial content of manganese is
much larger than that of sulfur, manganese element always remained in
excess, the consumption rate of manganese caused by formation of MnS
is much smaller than its growth rate, thereby the total manganese con­
tent is increased, whereas the opposite occurred in the case of sulfur.
Furthermore, with the increase of sulfur content from 78 to 1578
ppm, the corresponding solid fraction of MnS precipitation was
10
Materials Characterization 194 (2022) 112367
decreased significantly from 0.9609 to 0.3688. The results demonstrate
that the higher of sulfur content in the medium‑manganese steel, the
earlier will be the time for the MnS precipitation. The MnS in the
high‑sulfur manganese steel has sufficient growth time, resulting in the
increase of its final size, while the MnS in the low-sulfur manganese-
containing steel mainly precipitates at the end of solidification. There­
fore, the sulfur content in medium manganese steel can be considered as
a main step to control the precipitation size and amount of MnS, and the
sulfur content in molten steel should be strictly controlled during the
smelting process. Furthermore, it is evident from the EPMA mapping
image (Fig. 12c-d) that the dendrites are enriched with manganese and
sulfur element, which confirms the micro-segregation behavior in me­
dium manganese steel.
Based on the above analysis, Fig. 13 represents the precipitation
mechanism of MnS in manganese steel in which the primary Fe–Mn
dendrites grow gradually with the progress of solidification while the
solute elements as manganese and sulfur are rejected into the liquid
phase, as a result gradient of manganese content was developed, and
also the interdendritic region was enriched with sulfur atoms. The MnS
starts to nucleate in the residual liquid phase when the equilibrium
content of sulfur is reached, and it eventually evolved into the various
types of MnS with the addition of sulfur [37]. In case of low-sulfur steel,
a metastable segregation reaction occurs at the boundaries of Fe den­
drites, which leads to a large amount of spherical type I MnS. With the
increase of sulfur content, another type of MnS precipitation including,
rod-like MnS and the dendritic MnS are achieved, which indicates the
occurrence of eutectic reaction [38,39]. when the sulfur content was
further increased, a stable growth state of clustered MnS was combined
together precipitate. In addition, at the end of solidification, the newly
precipitated MnS in the residual liquid have not enough growth time,
and forms a lot of fine particles.
J. Chu et al. Materials Characterization 194 (2022) 112367

Fig. 11. (a-b) Pseudo-binary phase diagram of MnS and (c) the precipitation process of MnS with different phase transitions.

Fig. 12. (a) Solid and liquidus temperature, manganese and (b) sulfur content in liquid phase of manganese steels with different sulfur contents as the change of solid
fraction. (c-e) The EPMA images of S4 sample.

11
J. Chu et al. Materials Characterization 194 (2022) 112367

Fig. 13. The precipitation mechanism of MnS in manganese steel.

Fig. 14. (a) Solid and liquidus temperature, (b) difference in solid-liquid temperature of steels with different manganese contents. (c) The manganese and (d) sulfur
contents in liquid phase of steels with different manganese contents with the change of solid fraction.

4.2. The effect of manganese content and cooling rate on evolution and
growth of MnS
To further explore the evolution mechanism of MnS in medium sulfur
steel (sulfur content about 200 ppm) with different manganese content,
the solidification simulation has also been employed. As shown in
Fig. 14a, with the increase of manganese content from 0.24% to 32.93%,
the solidus temperature was decreased from 1432 ◦ C to 1004 ◦ C, liq­
uidus temperature was decreased from 1533 ◦ C to 1372 ◦ C, respectively.
Correspondingly, the temperature deviation between solid and liquid
phases was increased from 101 ◦ C to 368 ◦ C, as shown in Fig. 14b.
Similarly, the content of manganese and sulfur in the liquid phase
increases with the increase of the solid fraction due to the segregation of
elements (Fig. 14c, d), while the sulfur content decays after an inflection
point. It is noteworthy that the inflection point appears on the manga­
nese content curve for the M0 sample, indicating that the manganese
content controls the precipitation of MnS. This phenomenon can be
attributed to the larger segregation ratio of sulfur than that of manga­
nese, and the content of sulfur in the residual liquid phase of the M0
sample is about twice than that of manganese, so there is no obvious
inflection point for the sulfur content curve. Furthermore, MnS precip­
itation solid fraction was 0.9868, 0.9421, 0.8622, 0.7541, 0.6244 in
steel with manganese content of 0.24%, 2.09%, 6.22%, 13.26% and
32.93%, respectively. The formation of MnS occurs preferentially earlier

12
J. Chu et al.
in high manganese steel, which is expected to facilitate the dissociative
eutectic reaction to precipitate the type III MnS with low surface energy
[25]. On the other hand, the growth time and size of MnS was increased
at the same solidification rate in high manganese steel, which was
caused by the extension of the solidification process. In case of steel
sample having manganese content <2.09%, the MnS was precipitated at
the end of solidification, and the size was relatively small.
In addition, the size and quantity of MnS in medium manganese steel
increases with the decrease of cooling rate based on the above results.
When the cooling rate is increased, the supersaturation of manganese
and sulfur in primary dendrites is also increased rapidly, as a result the
nucleation of MnS is accelerated along with the reduced growth time,
which dramatically decreased the final particle size. For furnace cooled
samples, the slow cooling rate causes a long solidification cycle, the
manganese and sulfur atoms are enriched at the core of MnS particles
and the MnS has enough time to grow into the large-sized rod-like in­
clusions. Therefore, the MnS in furnace-cooled samples presents a large
size, but in fewer numbers.
5. Conclusions
In the current work, various experimental techniques and solidifi­
cation simulation calculation were performed to investigate the effects
of sulfur content, manganese content and cooling rate on precipitation,
evolution, and growth behavior of MnS inclusions in medium/high
manganese, and precipitation and evolution mechanism of MnS was
confirmed by in situ observation experiment and micro-segregation
behavior. Simultaneously, the 3D spatial distribution and structural
characteristics of MnS inclusions are statistically analyzed based on a
new nondestructive X-ray micro-CT technique. The main conclusions
can be drawn as followings:
(1) For medium manganese steel with a manganese content of about
5%, the increase of sulfur content from 78 ppm to 1578 ppm
transforms the morphology of MnS from globular and spindle-like
(type I MnS) into large-sized rods (type II MnS) and dendritic
(type D MnS), along with the significant increase of number and
size of MnS. The difference in morphology depends on the type of
precipitation reaction occurs in manganese steel.
(2) Results of micro-CT show that MnS inclusions with different
morphologies are distinguished in reconstructed 3D space
through defining a series of parameters; the most of MnS in high
sulfur medium manganese steel appear to be aspherical,
including spindle, rod, irregular and cluster. Moreover, the pro­
portion of MnS with a mean feret diameter smaller than 40 μm is
>95%, which indicates the presence of a large amount of small
MnS particles.
(3) The precipitation sequence of MnS during solidification phase
transition of the medium manganese high sulfur steel could be
considered as: L → (L + δ + MnS) → (δ + MnS) → (δ + γ + MnS)
→ (γ + MnS) → (α + γ + MnS) → (α + MnS). The changes in
morphology and quantity were elucidated through the segrega­
tion of manganese and sulfur that led to MnS precipitation along
the boundaries of dendrites at the solid-liquid coexistence tem­
perature. When the sulfur content was increased from 78 to 1578
ppm, the solid fraction of MnS precipitation was decreased
significantly from 0.9609 to 0.3688, which caused nucleation of
MnS at an earlier stage.
(4) For medium sulfur steel (sulfur content about 200 ppm), when
the manganese content was increased from 0.94 to 13.26%, the
morphology of MnS was transformed from globular to rod shape
and irregular dendritic shape, and eventually transformed into
polyhedral shape MnS (type III), which is attributed to MnS oc­
curs in dissociative eutectic reaction preferentially earlier in high
manganese content steel with long solidification cycle. Besides,
the increases of manganese content with decreasing the cooling
13
Materials Characterization 194 (2022) 112367
rate also significantly increases, the number and size of the same
type α-MnS inclusions. As a result, steels with manganese content
>2.09%, the precipitation process of MnS could be determined by
the sulfur content.
Declaration of Competing Interest
The authors declare no conflict of interest.
Data availability
No data was used for the research described in the article.
Acknowledgements
This work was supported by the National Natural Science Foundation
of China (Grant No. 51874021 and 51874001).
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