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Kinetics Simulation of MnS Precipitation in Electrical
Steel
ckl,
Sabine Zamberger, and Ernst Kozeschnik
Martin Lu

In this work, the solid-state precipitation kinetics of manganese sulfides (MnS) particles in
ferrite during continuous deformation of electrical steel is investigated. Thermokinetic
simulations are carried out on basis of the software package MatCalc. The results are
compared with independent experimental results from literature. The mean radius
evolution of second phase MnS precipitates is numerically simulated as a function of the
heat treatment parameters time and temperature. The calculated results show good
agreement with the experimental measurements using a single set of simulation input
parameters.

Sulfur is a most common accompanying element in steel,
which can either form Fe-sulfides or segregate at grain
boundaries; both processes leading to embrittlement of
the materials at high and medium temperatures. In order
to prevent the negative effects of S, Mn is commonly
alloyed. This element has a greater affinity to S compared
to Fe. Manganese sulfide (MnS) inclusions improve the
machinability of the material and restrain primary grain
growth.[14] The majority of MnS precipitates nucleate at
austenite grain boundaries. In the presence of deforma-
tion, strain-induced dislocations provide additional het-
erogeneous nucleation sites for MnS.[1]
Electrical steels are iron-based alloys, which contain up
to 6.5 wt% Si and are tailored to exhibit certain properties,
such as a narrow magnetic hysteresis loop and high
magnetic permeability. The required textures and micro-
structures producing these properties are obtained by
control of grain boundary migration during grain growth
and recrystallization with a suitable dispersion of precip-
itate particles.[5] In particular, magnetic properties of iron-
silicon alloys for electrical applications have been
improved with such precipitates, most frequently of
MnS.[5,6] Because of that, understanding the kinetics of
MnS precipitation in electrical steels is important in the
design of rolling schedules and the selection of annealing
parameters.[7,8]
We present some selected data from literature for the
precipitation of MnS from supersaturated solution in the
[
] M. Lu ckl, E. Kozeschnik
TU Wien Institute of Material Science and Technology, Getreidemarkt
9, 1060 Vienna, Austria
Email: martin.lueckl@tuwien.ac.at
S. Zamberger
voestalpine Stahl Donawitz GmbH, Kerpelystrae 199, 8700 Leoben,
Austria
DOI: 10.1002/srin.201500041
already solidified electrical steel and corresponding
thermokinetic simulations using the software package
MatCalc (version 6.00/rel. 0.018).[911] The simulations are
utilizing the corresponding thermodynamic[12] and mobi-
lity databases.[13] The nucleation kinetics of precipitates is
evaluated from extended Classical Nucleation Theory
(CNT)[14,15] for multi-component systems.[9,16,17] The
interfacial energy is calculated using a generalized
broken-bond approach[18] taking into account the size[19]
and diffuse interface[20] effects. For the latter, a regular
solution critical interaction temperature is defined.
Further details of the equations implemented in MatCalc
have been described by Sonderegger and Kozeschnik.[20]
The growth kinetics is calculated from mean-field
evolution equations derived from the thermodynamic
extremum principle[9] and formulated in the framework of
the KampmannWagner numerical model.[10,21] The pre-
cipitation kinetics at grain boundaries is evaluated with the
model developed in ref.[22] Details on the application of the
approach to problems in precipitation kinetics in steel
have been reported repeatedly and the interested reader is
referred to, e.g., refs.[2325]
The main sources of experimental data for MnS
precipitation are reported for three electrical steel
grades,[1,7,26] where the growth and coarsening behavior
of MnS during hot deformation is investigated. Prior to
application of the load, each specimen was solution-
treated at 1300 8C for 30 min to dissolve the sulfides present
in the as-received plates. After this treatment, the speci-
mens were immediately cooled to test temperature and a
constant stress was applied. No precipitates were observed
in the specimens that were quenched before loading,
indicating that the particles were only formed during
deformation.[7] The chemical compositions of the elec-
trical steels are summarized in Table 1. The precipitation
domain (matrix phase) in the simulations for all alloys is
ferrite.

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Alloy C [wt%] Si [wt%] Mn [wt%] S [wt%] Prec. domain Reference

1 0.025 3.13 0.070 0.021 ferrite [1,7,26]

2 0.030 3.04 0.085 0.028 ferrite [1,7]
3 0.029 3.00 0.125 0.015 ferrite [1,7,26]

Table 1. Chemical composition of the investigated alloys.

In accordance with experimental evidence, in the
simulations, precipitation of MnS in ferrite is assumed to
occur simultaneously on grain boundaries and disloca-
tions.[1,7,26] Consequently, two separate populations of MnS
precipitates are considered in the simulations, which are
different in the type of nucleation site as well as diffusion
geometry for growth. One population is assumed to nucleate
at dislocations, the other one at grain boundaries. For the
latter, the evolution equations derived for grain boundary
diffusion geometry are utilized,[22] the precipitates
nucleated at dislocations are described with the standard
SvobodaFischerFratzlKozeschnik (SFFK) model[11] for
spherical diffusion fields. A dislocation density of 1012 m2 is
assumed for annealed ferrite.[27] In the simulation setup, no
effective volumetric misfit is selected for the mismatch
between precipitates and the matrix because MnS precip-
itates are reported to be incoherent to the Fe matrix. The
incoherent phase boundary can be considered as an ideal
source and sink for vacancies, thus relaxing any misfit
stresses rapidly. Additionally, excess vacancies introduced
by the continuous deformation process are assumed to aid
to this process, too. The initial grain size for ferrite is chosen
to be 2000 mm, in accordance with the experimental
investigations.[1]

Figure 1. Calculated and experimental mean radii of MnS located at grain boundaries in ferrite for various temperatures.

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Sun et al.[7] propose that the Mn diffusivity in the
present family of alloys is lower compared to low-Si alloys
due to attractive chemical interaction between Si and Mn.
In line with this suggestion, the diffusion coefficient of
Mn used in the present simulations is taken one order of
magnitude lower compared to the value determined in
ref.[28] The interface energy reduction between MnS and
matrix due to interface dilution is accounted for in the sense
of the model developed in ref.[20] with a regular solution
critical temperature of 2400 K. The substructure evolution
is modeled within the framework of the SherstnevLang
Kozeschnik ABC model.[29] Furthermore, at lower temper-
atures, we observed that it is necessary to reduce the total
number of nucleation sites at dislocations to get agreement
with experimental data. This effect is incorporated in a factor
termed as nucleation site efficiency. Unless otherwise
stated, all simulation input parameters are used with their
default values provided by MatCalc.[911] All simulations are
performed with the same identical set of simulation input
parameters.
Figures 1 and 2 show the calculated radius versus time
curves of MnS precipitation in the three different alloys at
temperatures of 800, 900, and 1000 8C. The experimental
Figure 2. Calculated and experimental mean radii of MnS located at dislocations in ferrite for various temperatures.
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data are displayed as circles, triangles, and squares,
depending on the test temperature. Figure 1 summarizes
simulation results for MnS precipitates located at grain
boundaries, whereas precipitates at dislocations are shown
in Figure 2.
The simulations agree well with the experimental
information. At higher testing temperatures, nucleation
at grain boundaries is dominant.[7] With decreasing
temperature, nucleation on dislocations becomes more
prominent. Apparently, the slope of the curves is in good
agreement with the experimental data, thus, suggesting
that the physical mechanism is captured correctly in our
modeling. Sun et al.[1] describe these mechanisms with a
phenomenological model.
In the present work, we have developed a numerical
model for the description of the precipitation kinetics of
MnS during hot deformation in electrical steels. The
MatCalc simulations clearly demonstrate that MnS for-
mation occurs by simultaneous precipitation at grain
boundaries and dislocations. The required input param-
eters for the simulations are identified. One identical
simulation set up is utilized for all calculations, with the
parameters summarized in Table 2.
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Unit
Nucleation model
Regular solution critical temperature K 2400
Grain size mm
Diffusion enhancement
2
Dislocation density m 1  10
ABC-model
Nucleation site efficiency
Table 2. Evaluated parameter set of MnS precipitation in electrical steel using MatCalc.
Acknowledgements
The research program of K1-MET, which has been
financially supported within the Austrian competence
centre program COMET by the Federal Ministry of
Economy, Family and Youth; by the Federal Ministry for
Transport, Innovation and Technology; by the provinces of
Upper Austria, Styria and Tyrol; by the Styrian Business
Promotion Agency and by the Tiroler Zukunftsstiftung, has
its focus on the modeling and simulation of metallurgical
processes, including metallurgical raw materials and
refractoriness with the goal of an optimal process control
with respect to product quality, zero waste, and the
minimization of energy and raw materials.
Received: February 3, 2015;
Published online: August 27, 2015
Keywords: MnS precipitation; thermokinetic simulation;
electrical steel
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