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Kinetics Simulation of MnS Precipitation in Electrical
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

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

2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim steel research int. 87 (2016) No. 3 271

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

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

272 steel research int. 87 (2016) No. 3 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Sun et al.[7] propose that the Mn diffusivity in the data are displayed as circles, triangles, and squares,
present family of alloys is lower compared to low-Si alloys depending on the test temperature. Figure 1 summarizes
due to attractive chemical interaction between Si and Mn. simulation results for MnS precipitates located at grain
In line with this suggestion, the diffusion coefficient of boundaries, whereas precipitates at dislocations are shown
Mn used in the present simulations is taken one order of in Figure 2.
magnitude lower compared to the value determined in The simulations agree well with the experimental
ref.[28] The interface energy reduction between MnS and information. At higher testing temperatures, nucleation
matrix due to interface dilution is accounted for in the sense at grain boundaries is dominant.[7] With decreasing
of the model developed in ref.[20] with a regular solution temperature, nucleation on dislocations becomes more
critical temperature of 2400 K. The substructure evolution prominent. Apparently, the slope of the curves is in good
is modeled within the framework of the SherstnevLang agreement with the experimental data, thus, suggesting
Kozeschnik ABC model.[29] Furthermore, at lower temper- that the physical mechanism is captured correctly in our
atures, we observed that it is necessary to reduce the total modeling. Sun et al.[1] describe these mechanisms with a
number of nucleation sites at dislocations to get agreement phenomenological model.
with experimental data. This effect is incorporated in a factor In the present work, we have developed a numerical
termed as nucleation site efficiency. Unless otherwise model for the description of the precipitation kinetics of
stated, all simulation input parameters are used with their MnS during hot deformation in electrical steels. The
default values provided by MatCalc.[911] All simulations are MatCalc simulations clearly demonstrate that MnS for-
performed with the same identical set of simulation input mation occurs by simultaneous precipitation at grain
parameters. boundaries and dislocations. The required input param-
Figures 1 and 2 show the calculated radius versus time eters for the simulations are identified. One identical
curves of MnS precipitation in the three different alloys at simulation set up is utilized for all calculations, with the
temperatures of 800, 900, and 1000 8C. The experimental parameters summarized in Table 2.

Figure 2. Calculated and experimental mean radii of MnS located at dislocations in ferrite for various temperatures.

2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim steel research int. 87 (2016) No. 3 273

Unit MnS [gb] MnS [disl]

Nucleation model Ortho-equil. Ortho-equil.

Regular solution critical temperature K 2400 2400
Grain size mm 2000 2000
Diffusion enhancement 0.1 0.1
Dislocation density m 1  10 12
1  1012
ABC-model A 50/B 2/C 1106 A 50/B 2/C 1106
Nucleation site efficiency 1000 8C : 1
900 8C : 0.5
800 8C : 0.1

Table 2. Evaluated parameter set of MnS precipitation in electrical steel using MatCalc.

Acknowledgements [9] J. Svoboda, F. D. Fischer, P. Fratzl, E. Kozeschnik,

Mater. Sci. Eng. A 2004, 385, 166.
The research program of K1-MET, which has been
[10] E. Kozeschnik, J. Svoboda, F. D. Fischer, P. Fratzl,
financially supported within the Austrian competence
Mater. Sci. Eng. A 2004, 385, 157.
centre program COMET by the Federal Ministry of
[11] E. Kozeschnik, J. Svoboda, F. D. Fischer, CALPHAD
Economy, Family and Youth; by the Federal Ministry for
2004, 28, 379.
Transport, Innovation and Technology; by the provinces of
[12] E. Povoden-Karadeniz (Ed.), Thermodynamic
Upper Austria, Styria and Tyrol; by the Styrian Business
Database ME-Fe1. 000. tdb, 2014.
Promotion Agency and by the Tiroler Zukunftsstiftung, has
[13] E. Povoden-Karadeniz (Ed.), Diffusion Database
its focus on the modeling and simulation of metallurgical
mc_fe_v0. 006. ddb, 2014.
processes, including metallurgical raw materials and
[14] E. Kozeschnik, Modeling Solid-State Precipitation,
refractoriness with the goal of an optimal process control
Momentum. Press, New York, USA 2013.
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[15] K. Russell, Adv. Colloid Interface Sci. 1980, 13, 205.
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[16] K. Janssens, G. Frans, D. Raabe, B. Nestler,
Received: February 3, 2015; E. Kozeschnik, M. Miodownik, Computational
Published online: August 27, 2015 Materials Engineering - An Introduction to
Microstructure Evolution, Elsevier Academic Press,
Keywords: MnS precipitation; thermokinetic simulation; Oxford, UK 2007.
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