Received: 2 January 2024 Revised: 23 February 2024 Accepted: 20 March 2024

DOI: 10.1002/eng2.12892

REVIEW

A review of research on MnS inclusions in high-quality steel

Yan Song Hainan Zhang Lei Ren

School of Materials and Metallurgy, Inner

Mongolia University of Science and Abstract
Technology (IMUST), Baotou, China MnS which has good plasticity is a non-metallic inclusion commonly found in
steel. For most steel types, the size, shape, and distribution of MnS have a signifi-
Correspondence
Lei Ren, School of Materials and cant influence on the properties of steel. The large-sized MnS inclusions disrupt
Metallurgy, Inner Mongolia University of the continuity of the steel and cause the anisotropy in steel. The result is a decline
Science and Technology (IMUST),
Baotou 014010, China.
of steel’s overall performance. In contrast, the small-sized MnS inclusions which
Email: [email protected] in the shape of spherical or spindle in steel can diminish the incidence of thermal
embrittlement and improve the machinability of steel. The morphology of MnS
Funding information
2023 Young Science and Technology in steel is mainly affected by the ingredients of steel and heat treatment man-
Talents Development Project, ner. MnS inclusions in steel are present in spherical, polyhedral, dendritic, and
Grant/Award Number: NJYT23117;
irregular shapes. The precipitation behavior is mainly affected by the steel ingre-
Fundamental Research Funds for Inner
Mongolia University of Science & dients, heat treatment system, and other factors. This paper summarizes the
Technology, Grant/Award Number: latest research results about the factors affecting MnS inclusions and controlling
0406082229; National Natural Science
measures in high-quality steel in recent years.
Foundation of China, Grant/Award
Number: 52264045
KEYWORDS
high quality steel, inclusions, mechanical property, MnS

1 I N T RO DU CT ION

High-quality steel is primarily used in the automotive industry, mechanical manufacturing, and construction industry.
With the advancement of technology and industrial development, there is a constant demand for improved material
properties, necessitating higher quality steel to meet new application requirements. Additionally, key sectors such as
aerospace, automotive manufacturing, and others have stringent safety and reliability requirements for materials, leading
to corresponding increases in the quality standards for steel. MnS inclusions are one of the main factors affecting the
performance of high-quality steel. MnS inclusions generally have low hardness. During rolling and machining, MnS
inclusions are easy to extend into large-size long strips, which leads to anisotropic mechanical properties of steel. MnS
inclusions may serve as initiation sites for cracks, leading to crack propagation under stress and consequently reducing
the toughness of the steel. The elongated MnS inclusions formed during the solidification process are detrimental to
the mechanical properties of steel rails.1 It also reducing the plasticity of steel and disturbing the continuity of steel
matrix.2 The anisotropy of steel properties can be effectively improved by reducing the length of MnS inclusions and
the aspect ratio of MnS inclusions.3 MnS inclusions in steel can alleviate the sensitivity of hydrogen-induced cracks.4
MnS can be coated on the surface of oxide inclusions to reduce the damage caused by oxide inclusions.5 The purpose of
MnS inclusions is to improve the machinability of steel, retard grain growth, and promote the formation of intragranular
ferrite.6 Therefore, MnS inclusions are both harmful and beneficial to the properties of steel, which mainly depends on

This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the
original work is properly cited.
© 2024 The Authors. Engineering Reports published by John Wiley & Sons Ltd.

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2 of 21 SONG et al.

the size and morphology of MnS inclusions. In view of this, the factors affecting MnS inclusions and the modification
treatment of MnS inclusions are discussed comprehensively in this paper.

2 CAUSES O F MNS INCLUSIONS G ENERATION

Sulfur is usually regarded as a harmful element in most steels, and its segregation at grain boundaries significantly reduces
the properties of steels. Sulfur increases the cold brittleness of steel, making it more prone to fracture at low temperatures.
This is highly detrimental for certain steel materials used in specialized applications, such as components or structural
materials operating under low-temperature conditions. Because of the strong binding ability between manganese and
sulfur, proper amount of manganese is usually added to steel to reduce the harmful influence of sulfur. For non-calcium
treated steel, adding manganese to steel will preferentially form MnS inclusions and reduce the free sulfur content in
steel.7 Sulfur as a deleterious element needs to be removed in general steel grades. But in non-tempered steels which
different from ordinary steel grades, sulfur is the main free-cutting element in that, and its function is closely related to
MnS inclusions in steels.7 To obtain good machinability, it is necessary to add a certain amount of sulfur into steels to
make MnS inclusions small in size, diffusely distributed, and disperse in spherical or spindle shape.8

3 CLASSIFICAT ION O F MNS INCLUSIONS

The classification of MnS was discussed based on chronological order. In 1949, Sims et al.9 classified MnS in low carbon
aluminum steel into three categories based on morphology. Category I is spherical inclusions which randomly distributed,
single-phase or two-phase in non-aluminous deoxidized steels. Category II is tiny strips which distributed along grain
boundaries and small amount exists in aluminous deoxidized steels. Category III is angular or polyhedral inclusions
which irregularly distributed and existed in high-aluminous steels. In 1981, Ito et al.10 classified MnS into four categories
based on its two-dimensional morphology. Category I is spherical, category II is fan- or chain-shaped, category III is
polyhedral-shaped, and category IV is irregularly shaped, as shown in Figure 1. In 1995, Oikawa et al.11 studied respec-
tively the MnS morphology at 0.3% and 1.3% sulfur content, as well as classified MnS into three categories according to
morphology: category I is monotectic MnS; category II is eutectic MnS; and, category III is irregular polyhedral MnS. It
can be drawn that category I sulfides are generated by sub-stable monotectic reactions, category II sulfides are generated
by stable eutectic reactions, and class III sulfides are generated by nonstationary eutectic (pseudo-eutectic) reactions as
shown in Figures 2 and 3. In 2013, accordance with the precipitation types of MnS in steel, Brandaleze et al.12 classified
it into three categories. Category I spherical composite sulfides precipitated in the liquid phase, Category II sulfides pre-
cipitated along the dendrites, and Category III block sulfides precipitated in the solid phase. Among them, category II
sulfides belong to the sulfides in which Mn and S elements are enriched in the liquid phase between the dendrites dur-
ing solidification and precipitated along the grain boundaries, which are long and easily deformed and can destroy the
continuity of the steel matrix.

FIGURE 1 Classification of MnS inclusions by Ito et al.10 (A) Category I; (B) Category II; (C) Category III; (D) Category IV.
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SONG et al. 3 of 21

FIGURE 2 Main phase MnS morphology by Oikawa et al.11 (A1), (A2) Spherical MnS; (B1), (B2) Dendrite MnS; (C1), (C2) Polyhedral
MnS.

FIGURE 3 Two-phase MnS morphology by Oikawa et al.11 (A1), (A2) Monotectic MnS; (B1), (B2) Rod shaped eutectic MnS; (C1), (C2)
Irregular eutectic MnS.

4 EFFECT OF MNS INCLUSION ON STEEL PROPERTIES

4.1 Damage to steel by MnS inclusions

The precipitation of MnS, which occurs in most steels, has a significant impact on the high-temperature ductility of steel.
Because the high temperature ductility of MnS inclusions and the steel matrix is basically consistency. When steel rolling
or forging process, it easy along the metal extension direction into long strips of MnS and leading to a serious decline
in the transverse mechanical properties of steel. Yamamoto et al.13 found that during hot rolling, MnS inclusions that
extend into long strips which have a greater effect on the local ductility of the steel compared to the small-sized Al2 O3
inclusions. Hosseini et al.14 directly observed the separation behavior of MnS inclusions from the matrix in the tensile
process of medium carbon sulfur-containing steel samples. It was found that when the stress reached 20% of the tensile
strength, the interfacial separation behavior of MnS inclusions from the matrix began to occur in the transverse samples
as shown in Figure 4A.While the longitudinal specimens do not separate at the interface between MnS inclusion and
matrix during the tensile process. MnS inclusion firstly breaks inside the MnS inclusion, and the stress value is 90% of
the tensile strength, as shown in Figure 4B. In low-carbon steel, large and elongated MnS inclusions are the primary
factors causing the anisotropy of tensile ductility and impact toughness of rolled plates.15 In high-strength steel, MnS
inclusions significantly affect the microstructure and mechanical properties of the steel matrix. Refining MnS through
oxide inclusions can enhance the strength of the steel and suppress its anisotropy.16 In 304 stainless steel, the dissolution
of MnS inclusions is the first step. The second step involves intergranular corrosion caused by the dissolution of the
Cr-depleted zone. Finally, passivation occurs in the intragranular region.17

4.2 Benefits of MnS inclusions on steel

MnS inclusions have been used as effective inhibitors in oriented silicon steel for the first time. The dispersion of MnS
inclusions in steel can effectively inhibit the growth of secondary grains in the process of recrystallization, promote the
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4 of 21 SONG et al.

FIGURE 4 Separation of MnS from matrix during tensile process.14

growth of Gaussian phase grains, and enhance the magnetic properties of oriented silicon steel.18 Yang et al.19 proposed
that in the solidification process of liquid steel, small size or nano size MnS can promote nucleation of intragranular
ferrite and splitting austenite to refine the grain, which can improve the strength and toughness of steel. Wang et al.20
found that MnS coated with oxides as cores formed composite inclusions, which could offset the harmful effects of oxides
on the contact fatigue properties of steel. High speed heavy rail steel is highly sensitive to hydrogen white spots, but if it is
difficult to completely remove hydrogen from steel, a large number of studies have found that the presence of MnS in steel
can reduce the diffusion coefficient of hydrogen in steel.4,21 In non-tempered and sulfur-containing free-cutting steels,
MnS inclusions exert a notch effect during cutting and machining, making the chips easily breakable and improving the
machinability of the steel meanwhile reducing tool wear.8,22 An appropriate amount of MnS can serve as a grain boundary
refiner, aiding in improving the processability of steel, including machining and forming processes, thereby enhancing
production efficiency. A suitable quantity of MnS can result in the formation of uniformly distributed hard particles within
the steel, contributing to improved wear resistance and prolonged service life.

5 EFFECT OF MNS MORPHOLOGY O N STEEL PROPERTIES

Some Japanese scholars23 believe that: the shape control of MnS inclusions in steel is more important than reducing the
S content in steel, because excessive pursuit of steel cleanliness is uneconomical and technically challenging to meet
requirements. The performance of steel has an important connection with MnS inclusions. Different forms of MnS will
produce different effects. Because chain inclusions and long inclusions can cause defects in the steel, it is important to try
to control the MnS inclusions into fusiform or spherical shapes. In 1977 Segal et al.24 investigated the effect of MnS size
on its degree of deformation and showed that under the same deformation conditions, the small size MnS deformed less
than the large size MnS. Baker et al.25 came to the same conclusion through a large number of experiments. Academician
Yin research26 : the spindle-shaped inclusions (L/W ≤ 3) are not easy to deform during heat treatment. The transverse
mechanical properties of steel are basically stable, and it is a preferable inclusion form. Because strip sulfide with aspect
ratio more than 4:1 will not only destroy the continuity of steel matrix, but also cause cutting bonding, it is generally
believed that spherical or spindle sulfide with uniform distribution and fine grain is more beneficial to improve the cutting
performance of steel than long strip MnS inclusions.27,28 The results of Wang et al.29 showed that after the inclusion
denaturation, a large part of MnS changed from strip shape to spindle shape with the change of sulfide morphology, and
the section shrinkage and anisotropy of steel decreased by about 10% and 34%, respectively.

6 EFFECT OF CHEMICAL CO MPOSITION IN STEEL ON THE

M O RP H O LO GY O F M N S

6.1 Effect of elemental oxygen on MnS

Among the elements in steel, oxygen has the closest effect on MnS. Controlling oxygen content in steel is one of the main
methods to change the shape of MnS in steel. Due to the dissolution of oxygen, (Mn, Fe) (S, O) inclusions are formed.
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SONG et al. 5 of 21

FIGURE 5 Relationship between MnS inclusion morphology and oxygen content in steel.32

FIGURE 6 Relationship between length-width ratio and area of MnS inclusions and oxygen content in steel.33

The presence of these inclusions, which often exhibit poor shapes, significantly diminishes the deformability of MnS. This
control over the spherical shape of MnS after hot working is highly advantageous, particularly in enhancing the cutting
performance of steel.30 In 1949, Sims et al.9 found that when the oxygen activity in steel is high, MnS is easily modi-
fied to spherical shape, while when the oxygen activity decreases, MnS gradually transforms from spherical to chain and
irregular shape. Eeghem et al.31 demonstrated that in deoxidized steel, when the oxygen content (T[O]) exceeds 0.012%,
the first type of MnS inclusions form. These inclusions typically exhibit a multi-phase structure and assume a spheroidal
shape when subjected to high temperatures, thereby enhancing cutting performance. When T[O] ranges between 0.012%
and 0.008%, the second type of MnS inclusions develop, often appearing in a net or chain formation along grain bound-
aries. Conversely, when T[O] is below 0.008%, the third type of MnS emerges. This type lacks oxide precipitation, is
single-phase, easily deformable, but does not contribute positively to cutting performance. Xia et al.22 showed that when
oxygen content in steel is high, MnS formation changes from eutectic to monotectic, forming type I MnS; when oxygen
content is low and most of the MnS precipitation eutectic solidification ends, type II MnS is formed. When oxygen activ-
ity in steel is high, type I MnS gradually change from I to III with the decrease of oxygen activity and the increase of
sulfur and manganese activities,32 as shown in Figure 5. In cast steel, as the total oxygen content rises, the aspect ratio of
MnS inclusions decreases for a constant inclusion area. Conversely, the aspect ratio of MnS inclusions increases with the
area. Moreover, the impact of oxygen content on MnS inclusion morphology intensifies with increasing inclusion area,33
illustrated in Figure 6.
When the total oxygen content in steel is low, it is easy to form pure MnS inclusions with good plasticity. As shown
in Figure 7A, this thin strip of MnS inclusions will be significantly extended in the rolling process, affecting the mechan-
ical properties. When the total oxygen content in steel increases, the number density of inclusions containing Al2 O3
increases greatly. And the Al2 O3 core MnS heterogeneous nucleation complex inclusions increased in proportion, as
shown in Figure 7B, the average size of this type of inclusions is smaller and harder than the MnS inclusions alone, and
the possibility of deformation in the rolling process is less.34
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FIGURE 7 MnS inclusions and MnS-Al2 O3 composite inclusions in steel.34 (A) MnS inclusions; (B) MnS-Al2 O3 composite inclusions.

F I G U R E 8 Effect of different sulfur content on the morphology of MnS inclusions in steel.37 (A) Effect of different sulfur contents on
MnS morphology; (B) Formation of dendritic MnS morphology at 0.63% sulfur content.

6.2 Effect of manganese and sulfur elements on MnS

When the concentration of Mn and S in the interdendrite liquid exceeds the thermodynamic equilibrium solubility of
MnS in the steel, Mn and S in the steel tend to be separated and precipitated as MnS inclusions. Jianhua Chu et al.35
determined the precipitation process of MnS through sulfur content. The content of S in the steel plays an important role in
the precipitation time of MnS.36 Takada et al.37 found that when sulfur content in steel is 0.01%–0.04%, the spherical MnS
forms in the steel. When the sulfur content of steel is 0.05%, the elongated MnS forms in the steel. When the sulfur content
in steel reaches 0.1% and continues to increase, the polyhedral-shaped MnS forms in the steel, as shown in Figure 8A.
When the sulfur content reaches 0.63% and the manganese content is close to 2.88%, large-sized dendritic or skeleton-like
MnS will easily be formed in steel, as shown in Figure 8B. Oikawa et al.11 found that as the sulfur content in steel increases,
the precipitation temperature of MnS increases accordingly, and the more easily MnS precipitates. Wakoh et al.38 showed
that when sulfur content in steel ≤100 ppm, MnS selectively precipitated oxides with high sulfur capacity and low melting
point as nucleation, and when sulfur content in steel >100 ppm, all oxides may be the core of MnS precipitation. The
variation of MnS heterogeneous nucleation rate with sulfur content under different deoxidation conditions is shown in
Figure 9. The figure indicates that silicomanganate and manganese titanate promote heterogeneous nucleation of MnS
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SONG et al. 7 of 21

FIGURE 9 The influence of sulfur content on the nucleation rate of MnS under different deoxidation conditions.38

F I G U R E 10 Relationship between ω(Mn)/ω(S) and MnS spindle rate and inclusion number in steel.41

under low sulfur conditions. Conversely, Al2 O3 does not facilitate MnS nucleation heterogeneously. Under high sulfur
conditions, most deoxidation products effectively serve as cores for MnS formation. Kim et al.39 found that the dotted and
shell-shaped inclusions on the oxide surface in steels with high Mn content are MnS. The timing of MnS precipitation
can be managed by adjusting the manganese and sulfur mass fractions in steel, along with the degree of undercooling.
Specifically, decreasing the sulfur mass fraction and augmenting steel undercooling can postpone the precipitation of
MnS inclusions.40 It was found that the manganese and sulfur content in steel has a great influence on the number and
morphology of MnS inclusions in steel. It can be seen in Figure 10, with the increase of the manganese to sulfur ratio, the
spindle-shaped proportions in steel increases meanwhile the overall number of inclusions in steel decreases constantly.41
In free-cutting steels, a suitable Mn, S mass fraction ratio not only controls the MnS shape, but also improves the cutting
process by avoiding the formation of (Mn, Fe)S that is unfavorable for cutting.42

6.3 Effect of calcium elements on MnS

Calcium in steel can change the shape, size, and distribution of MnS inclusions. This is because calcium has a stronger
affinity for oxygen and sulfur than common elements, which will take away oxygen and sulfur in steel and generate CaO
and CaS. The increase of calcium content can promote the transformation of MnS from strip shape to spindle shape.
The shape and size of the inclusions are greatly affected by the ratio of the mass fraction of calcium and sulfur in steel.
When the ratio is greater than 0.2, the MnS change into a spindle shape, and the average size of the inclusions decreases
with the increase of the ratio.43 Elemental calcium stands as the most frequently employed modifier for MnS inclusions.
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F I G U R E 11 Formation of spherical composite inclusions by sulfide encrusting oxides.44

F I G U R E 12 Relationship between calcium content and MnS shape and aspect ratio.45 (A) Variation of calcium content on MnS shape;
(B) Variation of calcium content on MnS aspect ratio.

Experimental evidence suggests that adding calcium alloys to steel can induce the transformation of MnS from elongated
strips to spindle-shaped forms.3 According to relevant literature reports,44 after the steel is treated with calcium, the
surface of oxide inclusions (Al2 O3 , CaO) will be coated with MnS and CaS precipitated during the cooling process, as
shown in Figure 11. The composite inclusions are in the shape of fusiform or spherical, which helps to reduce the influence
of MnS on steel properties and improve the performance of steel. In 1997, Blais et al.45 found that with the increase of
ω(Ca)/ω(S) ratio, MnS changed from elongated shape to spindle shape, and the average length-diameter ratio of inclusions
decreased. With the increase of Ca content in steel, the solid solution of uniform distribution of Ca in sulfide gradually
increased, thus Ca played a role in solid solution strengthening. As shown in Figure 12A, it is this solution strengthening
that increases the hardness of the inclusions and makes the MnS inclusions not easily deformed, changing from long strip
shape to spindle shape. As shown in Figure 12B, spheroidization of MnS can be achieved when the calcium content of
sulfide is between 0.7% and 2.0% (1 < L/W ≤ 3). The increase of calcium content in sulfide has no obvious effect on the
formation of MnS. As shown in Figure 13A. The MnS without calcium treatment presents in an elongated shape. So it
is appropriate to control the content of calcium in sulfide between 0.7% and 2.0%. Kanisawa et al.46 added Ca into the
steel, so that (Ca, Mn)S was mainly generated in the steel, and the high temperature plasticity of sulfide was significantly
reduced, as shown in Figure 13B. Moreover, through calcium treatment, MnS inclusions in the steel were mainly in the
shape of spindles rather than long strips, so that the influence of MnS inclusions in steel on steel performance was less.
Qiao et al.47 found that when the calcium content of sulfide exceeds 0.7%, the length-diameter ratio of sulfide is less than
3, inducing the transformation of MnS from elongated to fusiform, and showed a quantitative relationship between the
calcium content of sulfide and the length-diameter ratio of MnS (L/W): L/W = 1.68 + 0.91/Ca. Yao et al.3 found that MnS
in untreated samples were mainly fine strips and clustered. Treatment with calcium reduced the number of fine sulfide
strips, resulting in a higher proportion of spherical and evenly distributed MnS inclusions. Moreover, the proportion of
MnS inclusions with a length-to-diameter ratio in the range of 1–2 significantly increased in billets treated with calcium.
The rolled steel with MnS inclusions is more concentrated in the interval of 1–3 in length-diameter ratio.
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SONG et al. 9 of 21

F I G U R E 13 Morphology of MnS in steel before and after calcium treatment.46 (A) Morphology of MnS before calcium treatment; (B)
Morphology of MnS after calcium treatment.

F I G U R E 14 Effect of carbon content on morphology and area of MnS inclusions.51 (A) The effect of carbon content on the
morphology of MnS; (B) The effect of carbon content on the area of MnS.

6.4 Effect of carbon element on MnS

Sims48 and Eeghem31 investigated the relationship between MnS morphology and acid-soluble aluminum in steel at
different carbon contents, the main difference between the two is that Sims found that the region of presence of the
elongated MnS widens with increasing carbon content, while the opposite results were obtained by Egehem. Fredriksson
et al.49 found that in the carbon-free Fe-Mn-S alloy, only the monoectic reaction existed, resulting in the formation of
spherical and elongated MnS. In the alloy containing 0.2% carbon, the MnS weakly crystallized from the liquid under the
condition of slow cooling, while in the alloy containing 1% carbon, the crystallization characteristics were strengthened
when the carbon content increased. It crystallizes completely and forms only polyhedral-shaped MnS. Ao et al.50 studied
that the upper limit of sulfur content in steel can be relaxed appropriately by adjusting the addition of alloying elements
to ensure a certain carbon content and a suitable ω(Mn)/ω(C). Chen et al.51 found that with the increase of carbon content
in steel, the proportion of spherical MnS inclusions in manganese steel gradually increase, while the proportion of strip
MnS inclusions gradually decreases, and the total area of inclusions gradually decreases, as shown in Figure 14.

6.5 Effect of aluminum element on MnS

Sims et al.48 found that in oxygen-containing steels, the MnS morphology changes from spherical to tiny strips and finally
to polyhedral when Al varies from 0.005% to 0.15%, namely, the Al content in the steel has a strong influence on the MnS
shape. Lei et al.52 investigated nonmetallic inclusions in Al-deoxidized steel. They discovered that 98% of the inclusions
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F I G U R E 15 Relationship between MnS aspect ratio and tellurium content in steel.56

in the steel were diffusely distributed, consisting of MnS and MnS-Al2 O3 composite inclusions. Morphologically, the MnS
inclusions appeared angular and likely belonged to polyhedral structures.

6.6 Effect of tellurium element on MnS

Tellurium is a highly surface-active element that effectively reduces the shear resistance during steel deformation and
produces denaturation and modification of MnS.53 When tellurium is added to steel, the dissolved tellurium elements dis-
solve into MnS inclusions. After reaching solid solution saturation, tellurium forms MnTe with Mn, and MnTe aggregates
and wraps MnS. Lattice distortion occurs when MnS are wrapped, resulting in the increase of spherical and elliptic MnS
and the decrease of strip and chain MnS in steel.54 Zhang et al.55 discovered that adding tellurium to steel leads to the for-
mation of a white Fe-Mn-Tellurium composite phase around MnS inclusions. This addition also induces spheroidization
of MnS by facilitating solid solution formation between MnTe and MnS inclusions. Bai et al.56 investigated the modifica-
tion impact of MnS inclusions by adding high-purity tellurium powder to 20CrMnTi steel. Figure 15 demonstrates that the
tellurium treatment reduced the aspect ratio of inclusions in the steel from 3.17 to 1.83, highlighting a more pronounced
spheroidization effect. Projak et al.57 found that the denaturation treatment of MnS morphology by tellurium elements is
less reliant on the steel’s oxygen content. Additionally, spheroidizing MnS inclusions through tellurium element addition
enhances the steel’s machinability and cutting performance.

6.7 Effect of rare earth Ce on MnS inclusions

Since the affinity between sulfur and rare earth is greater than Mn, adding an appropriate amount of rare earth to steel will
form Rex Sy . Because of its unique electronic structure of 4f layer and strong chemical activity, rare earth Ce is widely used
in the fields of inclusion reforming, steel purification and solidification structure control.58 As MnS inclusions precipitate
out during solidification, previous studies have shown that adding Ce can refine MnS inclusions in steel. The mechanism
of Ce action is the heterogeneous nucleation effect of high melting point rare earth inclusions on primary phase. The
results of Li et al.59 showed that after adding the appropriate amount of rare earth Ce, the precipitation of MnS in the steel
was effectively inhibited and played a well role in the metamorphic inclusions. Wang et al.60 showed that the MnS size
of high-strength IF steel without rare earth Ce was significantly extended during the rolling process, about 10 μm. The
addition of rare earth forms S—O—Ce type inclusions with spherical morphology and size of 2–5 μm and independent
dispersion distribution, which has little effect on the continuity of steel microstructure and is beneficial to the improve-
ment of steel performance. Wang et al.61 studied the addition of rare earth Ce in EH40 ship plate steel, and found that
with the increase of Ce content in steel, the MnS inclusions precipitates with Ti-Ce oxide as the core are spherical, and
the refining effect of Ce on inclusions is obvious. The size of inclusions larger than 4 μm decreases significantly, and the
percentage of submicron inclusions increases. Li et al.61 found that the thermodynamic order of the possible inclusions
generated in steel after the addition of rare earth Ce elements was CeAl2 O3 > Al2 O3 > Ce2 O3 > MnS. The rare earth ele-
ment Ce affects the morphology and size of sulfur and oxygen inclusions, leading to diffuse spheroidization within the
steel matrix. The size of most inclusions is controlled within 2 ∼ 3 μm, which improves the performance of the steel. An
et al.62 discovered that elevating the rare earth Ce content in steel decreased CeAlO3 -like inclusions while increasing the
 25778196, 2024, 5, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/eng2.12892 by Cochrane Israel, Wiley Online Library on [19/05/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
SONG et al. 11 of 21

number of Ce2 O2 S-type inclusions. Additionally, the average inclusion size decreased from 2.83 to 2.66 μm with a rise in
Ce content from 0.015% to 0.028%.

7 EFFECT OF HEAT TREATMENT REGIME ON MNS INCLUSIONS

7.1 Effect of temperature and heating rate on MnS

After heat treatment, the size and morphology of MnS inclusions in solid steel vary with temperature, and MnS inclusions
of suitable morphology (spindle-shaped and nearly spherical) can be obtained to reduce their ductility during rolling
process.5,63 In 1981, Macfarland et al.64 found that rolled steel samples held at 925◦ C for varying 0–30 h were found to
have long strips of MnS gradually splitting into spherical or granular shapes, as shown in Figure 16. In 1996, Lou et al.65
deformed the MnS inclusions at 1000–1050◦ C by heat treatment, which was able to reduce the aspect ratio of MnS and
thus improve the transverse properties of the steel. In 2011, Wang et al.66 found that the number of MnS inclusions larger
than 5 μm decreased significantly when the heat treatment temperature was held at 900–1300◦ C for 2 h. It was found
that the large-size MnS split into multiple particles at a heating rate <2 K/S. When the heating rate increased to 6 K/S
and 10 K/S, the large-size elongated MnS no longer split, the low heating rate favors the splitting of large-sized MnS into
spheres. In 2016, Zhang et al.67 studied the influence of different heating temperatures and holding time at 1200–1400◦ C
on MnS inclusions in heavy rail steel. The test results showed that large inclusions with long MnS in rail were divided into
particles with smaller size and thickness. The number of MnS inclusions larger than 80 μm decreased, and the number of
MnS inclusions smaller than 5 μm increased. Murty et al.68 studied the morphological changes of polyhedral-shaped MnS,
and after holding at 1310◦ C for different times, the MnS inclusions changed from long blade-like to short thick rods shape,
ellipsoidal and spherical shapes in order, as shown in Figure 17. The inclusions in steel before heat treatment are generally
flocculent and long irregular morphology, and after heating to 1200◦ C MnS transforms into ellipsoidal inclusions and
small particle size inclusions near spherical shape, as shown in Figure 18. High temperature heating can significantly
promote the transformation of inclusions morphology to spherical shape in steel, and it has a significant effect on reducing
the number of large size MnS inclusions in steel.33 Shao et al.66 found that MnS inclusions in steel increased as the heat
treatment temperature continued to rise. At the same time, with the increase of the temperature in the steel, the large
size and slender MnS inclusions continue to split, and it is also found that the lower heating rate (≤2 K/S) is conducive
to the modified MnS to be fusiform or nearly spherical, as shown in Figure 19. Park et al.69 also concluded by their study
that low heating rate is favorable for the splitting of large size long strips of MnS. Qi et al.70 found that the morphology
of MnS inclusions changed with increasing temperature, When <600◦ C, MnS inclusions did not change significantly;
when 600–870◦ C, spherical transformation occurred; when >870◦ C, the area of MnS inclusions began to increase; as
shown in Figure 20. When >1100◦ C, MnS inclusions did not increase significantly. When the temperature in the steel
is close to 1200◦ C, the MnS inclusions grow up and become round obviously,as shown in Figure 21; when it is close to

F I G U R E 16 Changes of MnS morphology at 925◦ C for different time.64 (A) The morphology of MnS of the original rolled sample; (B)
The morphology of MnS after holding at 925◦ C for 5 h; (C) The morphology of MnS after holding at 925◦ C for 10 h; (D) The morphology of
MnS after holding at 925◦ C for 20 h; (E) The morphology of MnS after holding at 925◦ C for 30 h.
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12 of 21 SONG et al.

F I G U R E 17 Morphology changes of MnS inclusions in steel at 1310◦ C for different holding times.68 (A) The morphology of the
original rolled material MnS; (B) The morphology of MnS after holding at 1310◦ C for 0.5 h; (C) The morphology of MnS after holding at
1310◦ C for 10 h; (D) The morphology of MnS after holding at 925◦ C for 100 h.

F I G U R E 18 Morphological changes of MnS before and after heat treatment at 1200◦ C.66 (A) Morphology of MnS before heat
treatment; (B) Morphology of MnS after heat treatment.

1300◦ C, the size of MnS becomes large and spherical; when it is close to 1400◦ C, there is a large amount of liquid phase
around MnS, and MnS begins to redissolve in the steel matrix. Following heat treatment, the size and morphology of MnS
inclusions in solid steel vary with temperature. High-temperature heating significantly promotes the transformation of
inclusion morphology towards a spherical shape, effectively reducing the quantity of large-sized MnS inclusions in the
steel. Low heating rates (≤2 K/S) are conducive to altering the morphology of MnS inclusions. The evolution of MnS
inclusion morphology progresses from elongated, to elliptical, and eventually to spherical shapes. MnS inclusions in
steel form elliptical shapes at around 1200◦ C, with small particle sizes approaching spherical shapes. However, at higher
temperatures, MnS inclusions increase in size and gradually dissolve.

7.2 Effect of cooling method on MnS inclusions

The limiting factors for the formation of MnS inclusions are the Mn and S concentration products and temperature.
Under the condition of constant Mn content, the only way to reduce the aggregation of Mn and S at the solidifica-
tion front and thus further reduce the size and the number of precipitated MnS inclusions is to reduce the S content
and use strong cooling.71 Kinetic analysis shows that increasing the cooling rate and improving the cooling intensity
 25778196, 2024, 5, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/eng2.12892 by Cochrane Israel, Wiley Online Library on [19/05/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
SONG et al. 13 of 21

F I G U R E 19 Effects of different heat treatment temperatures and heating rates on the morphology of MnS inclusions.66

F I G U R E 20 Morphology changes of MnS inclusions during continuous heating.70 (A) morphology of MnS at 15◦ C; (B) morphology of
MnS at 817◦ C; (C) morphology of MnS at 1075◦ C; (D) The morphology of MnS at 1177◦ C; (E) The morphology of MnS at 1271◦ C; (F) The
morphology of MnS at 1377◦ C.

during the solidification of the molten steel can control the timing and morphology of MnS precipitation and reduce
its size, thus reducing its harmful effects of the steel performance.67 Imagumbai et al.72 found that slow cooling favors
the formation of spherical MnS inclusions and generates elongated sulfides when the cooling rate is faster. Shao et al.8
investigated the effect of different cooling methods on the morphology of MnS inclusions after heat holding. MnS was
linear under furnace cooling conditions, chain-like under air cooling conditions, and ellipsoidal under water cooling
conditions. Some authors73 analyzed the MnS formation and concluded that increasing the cooling rate can reduce
the average radius of MnS, as shown in Figure 22. Tian et al.74 observed the morphology of MnS in water-cooled
and air-cooled samples by scanning electron microscopy, and took the average diameter of inclusions. The statisti-
cal results are shown in Figure 23. It can be seen that the size of MnS in air-cooled samples is larger than that in
water-cooled samples.
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14 of 21 SONG et al.

F I G U R E 21 Solid solution of MnS inclusions at 1175◦ C.70

F I G U R E 22 Relationship between cooling rate of steel and average radius of MnS.73

F I G U R E 23 Distribution of MnS diameter in samples with different cooling modes.74

8 EFFECT OF OX IDES IN ST EEL ON MNS

8.1 Effect of high melting point oxides on MnS

Oxide metallurgy is a technique that alters the shape of MnS in steel, refines steel grain, and enhances steel toughness.
It achieves this by utilizing high melting point, finely dispersed oxide inclusions formed within the steel as nucleation
cores for MnS precipitates, thereby promoting ferrite formation in steel.75,76 With the introduction of the concept of oxide
metallurgy, the use of fine diffusely distributed oxides in steel to refine MnS formed during solidification has become a
hot spot for research. Figure 24 shows the schematic diagram of this method of refining MnS. The left side is a schematic
diagram of MnS extending along the rolling or forging direction in general sulfur-containing steel, with large size and
high aspect ratio. The right side is a schematic diagram of refining MnS using the oxide metallurgy method, with MnS
 25778196, 2024, 5, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/eng2.12892 by Cochrane Israel, Wiley Online Library on [19/05/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
SONG et al. 15 of 21

F I G U R E 24 Schematic diagram of MnS morphology using oxide nucleation.77 (A) morphology of MnS before oxide nucleation; (B)
morphology of MnS after oxide nucleation.

with small size, high number, uniform distribution, low aspect ratio, and the existence of oxide particles in most of the
core.77 It was found that different oxides (Mn-Si-O, Ti-Mn-O-N, ZrO2 , Al2 O3 ) have an effect on the precipitation of MnS,
which precipitates embedded on high melting point oxides, while the controlled cooling regime has an important effect
on the precipitation of MnS.78 In 1997, OiKawa et al.5 demonstrated that the addition of Ti to steel considerably decreased
the size of MnS inclusions. This reduction occurred because of the liquid state of (Ti, Mn) O, high sulfur content, and
nucleation growth along with MnS inclusions at the solidification front. In the same year, Gregg et al.79 concluded that TiO
exhibited a more potent nucleation effect. In 2001 Hasegawa et al.80 found that ZrO2 has a heterogeneous nucleation effect
on MnS in Fe-Si alloys and most of the MnS inclusions have ZrO2 inside. In 2003 Kim et al.81 found that SiO2 -MnO has a
high sulfur capacity due to the high sulfur content in the SiO2 -MnO oxide. In 2006, Liu et al.82 showed that titanium-rich
inclusions can promote the generation of ferrite in steel, which in turn contributes to the easier precipitation of MnS as a
heterogeneous core of oxide during the solidification of the molten steel. In 2007, Zhanbing Yang et al.83 discovered that
adding approximately 0.02% titanium to medium-carbon untempered steel leads to the formation of composite inclusions
containing titanium. These inclusions induce ferrite formation through heterogeneous nucleation. Guo et al.84 found that
ZrO2 has a favorable heterogeneous nucleation effect on MnS because it has similar lattice parameters as MnS. Sarma
et al.85 found that Al2 O3 inclusions tend to form clusters in steel and cannot be distributed diffusely, so they cannot be
used as an effective nucleation core for MnS.

8.2 Effect of deoxidation method on MnS

In recent years, a large number of oxide particles have been shown to have a good heterogeneous nucleation effect on
MnS. Many scholars both domestically and abroad have conducted various studies on the effect of different deoxidation
methods on MnS in steel. Figure 25 shows the effect of different oxides on the heterogeneous nucleation of MnS in low
sulfur steel. Figure 25 illustrates that various deoxidation methods yield different oxides, each with distinct effects on
MnS nucleation in steel. The composite deoxidation products formed by the composite deoxidizer result in over 80%
heterogeneous nucleation of MnS compared to single deoxidizers.86 In 1996, Wakoh et al.38 added Ti alone, Zr alone,
and composite Ti-Zr to low sulfur steel and found that Ti-Zr composite deoxidation had the best effect for increasing
the proportion of MnS nucleation. In 1999, Oikawa et al.87 investigated the effect of Al and Ti deoxidation products on
MnS morphology and quantity. They found that Ti oxide concentration was easily trapped at the solidification front,
promoting MnS nucleation at this location. In 2010, Yang et al.88 studied the effect of Ti and Al composite deoxidation on
precipitation of MnS inclusions and found that MnS morphology was mainly mosaic and encapsulated. In 2013, Li et al.89
investigated the effect of Al and Ti deoxidation on precipitation behavior of MnS in non-tempered steel. They concluded
that Ti’s deoxidation products were more favorable for heterogeneous nucleation of MnS while high Al content in steel
was not favorable for refinement of MnS inclusions. In 2015, Zheng et al.76 investigated the heterogeneous nucleation
effect of Ti-Mg deoxygenating products on MnS inclusions under different Ti/Mg ratios. They concluded that an optimal
molar ratio for Ti/Mg was between 0.05–0.2. In 2016, Wang et al.90 investigated the effects of aluminum, calcium, and
magnesium deoxidation processes on oxide nucleated MnS. As shown in Figure 26, the magnesium deoxidation process
was found to be the most effective for nucleating MnS inclusions.
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16 of 21 SONG et al.

F I G U R E 25 Effect of different deoxidation modes on MnS heterogeneous nucleation.86

F I G U R E 26 Different effects of Al, Ca, and Mg deoxidation processes on nucleating MnS.90 (A) The morphology of MnS after Al
deoxidation process; (B) The morphology of MnS after Ca deoxidation process; (C) The morphology of MnS after Mg deoxidation process.

F I G U R E 27 Cross section of Fe-13.54Cr-0.985Mn-XC-0.291Si-0.384Ni-(0.1/0.4)S system.91 (A) 𝜔s = 0.1%; (B) 𝜔s = 0.4%.

9 PRECIPITAT ION O F MNS INCLUSIONS IN S EVERAL TYPICAL

ST EEL FRADES

The results of the study91 showed that in sulfur-containing free-cutting steels, the formation temperature of MnS increases
with an increase in the Mn and S elements in the steel. MnS forms in the molten steel when the content of Mn and S
elements is too high. Additionally, the content variation of C and Cr elements has almost no effect on the formation
temperature of MnS. As can be seen from the phase diagram calculated in Figure 27, the MnS formation temperature
decreases slightly as the C content increases, and the effect of the change in elemental C content on the MnS formation
temperature is slight.
 25778196, 2024, 5, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/eng2.12892 by Cochrane Israel, Wiley Online Library on [19/05/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
SONG et al. 17 of 21

F I G U R E 28 Relationship between mass fraction of Mn and S and driving force of MnS nucleation chemistry in oriented silicon steel.92

F I G U R E 29 Change of precipitation amount of MnS inclusions with temperature during solidification.40

In manganese steel, the degree of influence on the formation temperature of MnS inclusions, in descending order, is
Mn, C, Si, P, S, Ni, while the influence of Cr, Mo, Cu can be ignored. In the actual production of 20Mn steel, implementing
lower limit control on the C and Si content can effectively inhibit the precipitation of MnS inclusions.51
Sun et al.92 found that the formation of MnS particles in oriented silicon steel is mainly influenced by the chemi-
cal driving force. The chemical driving force for MnS precipitation varies for different Mn and S contents, as shown in
Figure 28 With an increase in the mass fraction of S content, the chemical driving force also increases. Compared with
CaS, MgO, and other inclusions, MnS formation temperature is the lowest, but the extent of MnS precipitation increases
with the increase of S content of the molten steel.
Zhang et al.40 used the Factsage 6.4 thermodynamic calculation software, as shown in Figure 29, to calculate the
formation temperature of MnS inclusions in U75V steel as 1631 K, which is 63 K different from the equilibrium thermody-
namic parameters calculated as 1694 K. This method can accurately predict the precipitation behavior of MnS inclusions
and reduce the difficulty of thermodynamic analysis of MnS precipitation. When the formation temperature of MnS is
significantly lower than the steel’s phase transition temperature during solidification, MnS will mainly precipitate in the
supersaturated austenite. This can effectively reduce the size of MnS and control its morphology.

10 CO N C LU S I O N

1. Manganese and sulfur have a strong affinity for non-calcium-treated steel, the addition of manganese to the steel will
preferentially form MnS inclusions, in the form of spherical shape, polyhedral shape, irregular shape and other forms
 25778196, 2024, 5, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/eng2.12892 by Cochrane Israel, Wiley Online Library on [19/05/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
18 of 21 SONG et al.

existence in steel. MnS inclusions are generally low hardness, appearing in almost steel grades, which has great impact
for high temperature ductility of steel, because the high temperature ductility of MnS inclusions and steel matrix is
basically the same, in the steel rolling or forging process, easy along the metal extension direction into long strips of
MnS, resulting in a serious decline in the transverse mechanical properties of steel.
2. The use of high melting point, fine diffuse oxide inclusions as the nucleation core for MnS precipitates in steel can
promote the formation of ferrite and alter the shape of MnS in steel. This process can split austenite, refine the grain,
and improve the strength and toughness of the steel. In contrast, strip sulfide with an aspect ratio of more than 4:1
can damage the continuity of the steel matrix and cause bonding during cutting. It is generally believed that the dis-
tribution of uniformly sized, finer particles of spherical or spindle-shaped sulfide is more conducive to improving the
performance of steel compared to long strip MnS inclusions.
3. The precipitation behavior of MnS inclusions in steel is primarily determined by factors such as steel composition and
heat treatment regime. When the appropriate amounts of rare earths are added to the steel, the affinity between sulfur
and rare earths exceeds that of sulfur and manganese, resulting in the formation of Rex Sy .
4. Rare earth elements are widely utilized in reformation of inclusions, purification of steel, and control of solidification
organization due to their unique 4f-layer electronic structure and strong chemical reactivity. The size and morphology
of MnS inclusions in solid steel vary with temperature. By applying appropriate heat treatment, the desired morphol-
ogy of MnS inclusions (spindle and nearly spherical shape) can be obtained to decrease their ductility during the
rolling process.

AU THOR CONTRIBUTIONS
Lei Ren: Writing – review and editing. Yan Song: Writing – original draft. Hainan Zhang: Investigation.

ACKNOWLEDGMENTS
The authors are grateful for support from the National Natural Science Foundation of China (Grant No. 52264045), 2023
Young Science and Technology Talents Development Project (Young Science and Technology Talents NJYT23117) and
the Fundamental Research Funds for Inner Mongolia University of Science & Technology (Grant No. 0406082229).

CONFLICT OF INTEREST STATEMENT

The authors declare no conflicts of interest.

PEER REVIEW
The peer review history for this article is available at https://www.webofscience.com/api/gateway/wos/peer-review/10
.1002/eng2.12892.

DATA AVAILABILITY STATEMENT

The data that support the findings of this study are available from the corresponding author upon reasonable request.

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How to cite this article: Song Y, Zhang H, Ren L. A review of research on MnS inclusions in high-quality steel.
Engineering Reports. 2024;6(5):e12892. doi: 10.1002/eng2.12892