www.steel-research.

de

FULL PAPER

Conventional and Tailored MnBearing

Alloying Agents for the Production of High
Manganese Steels
Gereon Hils, Alexander Newirkowez, Michael Kroker, Ulrich Grethe,
Rune SchmidtJrgensen, Joachim Kroos, and KarlHeinz Spitzer

The industrial production of high manganese steel melts with approx. 1030 wt% Mn
makes high demands on the utilized Mnbearing alloying agents in terms of chemical
composition and costefficiency. Conventional Mnbearing alloying agents are reviewed in
this regard. A modified process route has been conceived for pyrometallurgical winning of
special silicomanganese grades tailored for high manganese steelmaking. For each
individual process step, namely manganese slag production, silicomanganese production,
and optional desiliconization of silicomanganese, results of labscale experiments are
discussed.

1. Introduction

1.2. Conventional MnBearing Alloying Agents for

Steelmaking

1.1. High Manganese Steels

High manganese steels exhibit special metal-physical
effects induced during their deformation, namely transformation-induced plasticity (TRIP-effect), twinning-induced plasticity (TWIP-effect), or shear band-induced
plasticity (SIP-effect).[1,7] These effects cause a unique
combination of ultra high strength and high ductility
yielding excellent processing and application properties.
Their occurrence is mainly controlled by the chemical
composition of the steel. Regarding major alloying
elements in high manganese steels, Table 1 gives the
approximate range of contents currently being studied.
High contents of aluminum and silicon not only contribute
to high strength and ductility but also cause a remarkable
decrease in density for certain grades.
In view of their attractive properties and the costefficient alloying concept, high manganese steels are
promising candidates for construction and engineering
materials in various applications, especially for lightweight
construction in automotive engineering.
[
] K. -H. Spitzer, G. Hils, M. Kroker, A. Newirkowez
Institute of Metallurgy, Clausthal University of Technology, RobertKoch-Strasse 42, 38678 Clausthal-Zellerfeld, Germany
Email: karl.heinz.spitzer@tu-clausthal.de
U. Grethe, R. Schmidt-Jurgensen, J. Kroos
Salzgitter Flachstahl GmbH, Eisenhuttenstrasse 99, 38239 Salzgitter,
Germany
DOI: 10.1002/srin.201400153

2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

In high manganese steels, manganese is that alloying

element with by far the highest contents. These are
considerably higher than in common steel grades
(Table 1). Therefore, impurities introduced by the utilized
Mn-bearing alloying agent dilute to a lesser extent in the
high manganese steel melt. Furthermore, the Mn-bearing
alloying agent holds a significant share on the overall
steelmaking costs. Thus, high demands in terms of
chemical composition and cost-efficiency are made on
Mn-bearing alloying agents utilized for high manganese
steelmaking. Conventional alloying agents are given in
Table 2.
Electrolytic manganese metal (EMM) features the
highest chemical purity, apart from selenium and hydrogen in some EMM grades. Selenium originates from the
aqueous winning electrolysis and largely evaporates
during alloying of steel melts thus causing potential
environmental and working place hazards in elemental or
compound form.[2] Hydrogen, also resulting from the
aqueous electrolysis, is a critical impurity, which many
high manganese steel grades are sensitive to. Its content is
lowered by effusion annealing of EMM. However, the
main drawbacks of a broad EMM utilization for high
manganese steel production are of economic nature:
Its price notably exceeds that for low-cost grades of
ferromanganese or silicomanganese even if related to the
manganese content. This becomes even more evident
since there are only few suppliers for electrolytic
manganese metal worldwide.

steel research int. 85 (2014) No. 9999

FULL PAPER

www.steel-research.de

Si

Mn

Al

01.2

03.5

1030

012

Table 1. Approximate contents of major alloying elements

currently being studied for high manganese steels (wt%).

High carbon ferromanganese (HC FeMn) and medium carbon silicomanganese (MC SiMn) are provided at
substantial lower prices in larger quantities than EMM.
Their main drawback is the purity level, which is adequate
for producing conventional steels with low manganese
contents, but proves insufficient for high manganese
steelmaking. This requires additional, subsequent steps for
steel refining, such as a decarburization in case of HC
FeMn (possibly MC SiMn) and a desiliconization in case of
MC SiMn. These refining steps have been evaluated
technical feasible but unprofitable by experiments as well
as application of a self-made process model.[35] In
addition, most grades of FeMn and SiMn have high
phosphorus contents of several thousand ppmw. Phosphorus has a pronounced detrimental effect on mechanical properties of high manganese steels and notably
impairs their weldability. A subsequent dephosphorization
of high manganese steel melts is not possible to a sufficient
extent.[4,6] As most commercial manganese ores and their
concentrates exhibit high phosphorus contents (Table 2),
choosing another ore grade for the production of FeMn or
SiMn is not a solution.
The low carbon grades LC FeMn and LC SiMn are of
minor relevance for high manganese steelmaking as
they are produced in small tonnages at prices currently
exceeding those for EMM.
Alloying
agent

The direct utilization of manganese ores in steelmaking,

although offering a significant cost advantage, is probably
inexpedient because a smelting reduction of manganese is
associated with extended process durations, large amounts
of slag and off-gas, a high energy input and doesnt solve
the phosphorus problem.
It is concluded that the solely or primarily utilization of
conventional FeMn or SiMn in high manganese steelmaking is unsuitable for two reasons: the high effort for
subsequent removal of carbon and silicon, and the
infeasibility of a sufficient steel dephosphorization. These
ferroalloys are thus restricted to small fractions in
feedstock blends, which mainly consist of EMM or special
tailored grades of SiMn.

2. Concept of a Modied Production Route

for Tailored SiMn
In order to provide an alternative to EMM for high
manganese steelmaking, a modified process route for the
industrial production of tailored grades of SiMn has been
developed.[7] Its first key objective is a suitable chemical
composition of these SiMn grades. This implies sufficient
purity, in particular regarding carbon and phosphorus, as
well as a Mn/Si-ratio adjusted to the final steel composition in order to avoid metallurgical work to be done
in the steel works. The second key objective is lower
costs per unit contained manganese compared to EMM.
Furthermore it is intended to use lean manganese ores,
which are available in large deposits at low costs, but rarely
utilized nowadays. Similarly, various Mn-bearing residuals
Price indexa)

Typical chemical composition (wt%)

Mn

Fe

Si

Others

rel. to
HC FeMn

rel. to HC FeMn
and Mn-content

HC FeMn

78

bal.

0.3

6.8

0.20

1.0

1.0

MC FeMn

81

bal.

0.3

1.2

0.15

0.12 N

1.5

1.4
b)

LC FeMn

82

bal.

0.6

0.2

0.15

0.12 N

(2.5)

(2.3)b)

MC SiMn

68

bal.

18

1.6

0.15

0.02 B, 0.2 Ti

1.0

1.2

LC SiMn

60

bal.

30

0.05

0.05

0.02 B, 0.2 Ti

(1.5)

(2.0)b)

EMMc)

99.8

0.001

0.002

0.002

0.001

0.3 Se, 0.0005 Hd)

2.0

1.6

0.2

0.3

e)

Mn-ore

49

f)

0.11

g)

0.008 B

b)

a)

As in February 2011;
Little information due to low production volume;
c)
Electrolytic manganese metal;
d)
Low-hydrogen grade assumed;
e)
Metallurgical grade, Gabon;
f)
South Africa: 0.020.08% P; Ukraine: 0.180.22% P; Others: 0.060.14% P;
g)
South Africa: 0.050.09% B; Gabon: 0.0070.008% B; Australia: 0.00050.0020% B.
b)

Table 2. Conventional Mn-bearing alloying agents.

steel research int. 85 (2014) No. 9999

2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.steel-research.de

such as dusts and slags accruing in production of high

manganese steels are to be recycled to decrease feedstock
costs and waste disposal. A scheme of the entire process
route is shown in Figure 1.
Its main feature is the pyrometallurgical winning of a
manganese slag (Mn-slag) as a high-grade feedstock for
subsequent production of tailored grades of SiMn. Based on
the considerable less thermodynamic stability of the oxides
of iron and phosphorus in comparison to those of
manganese, a selective solid-state carbothermal reduction
of iron and phosphorus to a metal phase is conducted
keeping most of the manganese in a partially reduced oxidic
state as MnO. Separation of metal and slag is achieved by
melting. This enables a simple process technique, a high
space-time yield and the coproduction of a liquid hot metal,
which may be refined to steel or sold to iron foundries. As
main product, a liquid MnOSiO2-slag with approx. 30
40 wt% SiO2 and low Fe- and P-contents is obtained.
The feedstock for Mn-slag production comprises an
adequate mixture of manganese ores and iron ores,
complex MnFe-ores or recycled Mn-bearing dusts and
slags. Further additions are carbonaceous reducing
agent in a stoichiometric quantity and SiO2. The latter
acts as a flux and additionally improves the selectivity

2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

German

Soviet

Duplex

practice

practice

practice

Feedstock

Fe-rich

Fe-lean

Fe-lean

Furnace

Blast
furnace

Electric
shaft

Electric
shaft

furnace

furnace

12301420

>1500
(assumed)

>1500
(assumed)

Type

Hot metal

FeMn

FeMn

Mn (wt%)

35

3075

7080

P (wt%)

0.10.7

15

0.150.30

Qty. (t/tslag)

1

0.10.3

12

[1012]

[8,9,13]

[8,14,15]

Temperature (8C)

Metal obtained

Selected references

Table 3. Compilation of literature data on various practices of

Mn-slag production.

steel research int. 85 (2014) No. 9999

FULL PAPER

Figure 1. Scheme of the conceived production route for various

tailored SiMn grades.

of the reduction due to its acidic character, which

increases the P2 O5 -activity and decreases the MnOactivity, thus yielding an improved P-reduction and a
limited Mn-reduction. SiO2 is also required for the
subsequent reduction of the Mn-slag to SiMn in order to
achieve a sufficient high silicon content in the SiMn
depending on its aimed carbon content. This feedstock
mixture, for instance, could be pelletized, solid-state
reduction may be performed in a rotary hearth furnace
and metal-slag separation could take place in a suitable
electric slag-melting furnace.
State of the art of Mn-slag production is covered in
several dozen, mainly older references mostly empirically
and on industrial scale (Table 3). There are essentially
three modes to operate the process (practices). They
differ from each other firstly in the metallic solvent utilized
for absorption of phosphorus and secondly in the extent
of phosphorus dilution in this solvent. The German
practice (authors nomenclature), using Fe-rich feedstock
and producing a Mn-bearing hot metal, was particularly
performed in German blast furnaces during the Second
World War to enrich lean domestic FeMn-ores for FeMnproduction. It may be operated under carbon saturation at
low temperatures, thus achieving extended iron reduction
but limited manganese reduction. The German practice is
in principle applied within the modified production route
described in the present work. On the other hand, if using a
feedstock low in iron, the phosphorus has to be solved in a
Mn-rich metal phase. Higher temperatures are necessary
for manganese reduction, whose extent is controlled by the
amount of reducing agent. In case of the Soviet practice
(authors nomenclature), as little manganese is reduced
as necessary for phosphorus solution, resulting in high

FULL PAPER

www.steel-research.de

phosphorus contents of approx. 15 wt% in the metal.

Indeed this metal is of little value, but only small amounts
of approx. 100300 kg per metric ton of Mn-slag are
generated thus limiting manganese losses. This practice
has mainly been applied in the former Soviet Union for
domestic Mn-ores being of particularly high phosphorus
and low iron contents. In case of the duplex practice,
considerably more manganese is reduced in comparison
to the Soviet practice in order to achieve a higher dilution
of phosphorus in the metal. In this way, approx. 12 t of HC
FeMn meeting commercial specifications can be produced
per metric ton of Mn-slag. This enables the coproduction
of the two valuable products HC FeMn and Mn-slag, which
denotes a compromise of phosphorus and manganese
distribution. Due to the extensive reduction of manganese,
the resulting Mn-slag contains less manganese compared
to the other practices. The duplex practice is state of the art
and currently performed at several smelters producing
both FeMn and SiMn.
Thus obtained Mn-slag serves as high-grade feedstock
for the subsequent carbothermal reduction to SiMn by
conventional means in an electric shaft furnace with
addition of coke and SiO2. These additions have to be lean
in phosphorus as the latter mainly passes into the SiMn.
The carbon content of the SiMn strongly decreases with
rising silicon content. This implies two different ways of
producing a tailored SiMn: For high manganese steels with
medium carbon contents, a tailored MC SiMn with
medium carbon content may be utilized. This MC SiMn
is directly produced from Mn-slag in one stage with an
adjusted Mn/Si-ratio.
On the other hand, high manganese steels with low
carbon contents require a tailored LC SiMn, which is low in
carbon. This is obtained in a two stage process: In the first
stage, LC SiMn with high Si- and corresponding low Ccontents is produced, optionally with addition of some
ferrosilicon to reach up to 30 wt% silicon in the metal. In
the second stage, this LC SiMn is desiliconized by selective
oxidation of silicon to achieve the desired Mn/Si-ratio.
Possible oxidizing agents are oxygen, high-grade manganese ores or a special type of Mn-Slag. The latter has been
used in the present work. This so called desiliconization
slag mainly consists of MnO and Al2O3 and is produced
similarly to abovementioned Mn-slag. Its utilization as
oxidizing agent in desiliconization of SiMn allows an
additional silicothermic reduction of MnO. Beside the
oxidizing agent, CaO is added for fluxing and enhancement
of desiliconization by lowering the SiO2-activity and
raising the MnO-activity. The degree of desiliconization
may be expanded down to approx. 1 wt% Si remaining in
the SiMn, although in that case large additions of oxidizing
agent and CaO are required and a lot of final slag is
generated.[8,9] Desiliconization by desiliconization slag or
Mn-ores may take place in the ladle or ladle furnace. For
desiliconization by oxygen a MOR-type reactor can be
used, whereby a combination of oxygen blowing and
addition of said desiliconization agents may also be

steel research int. 85 (2014) No. 9999

Mn-slag production
Feedstock
Ore mixture
Fe/Mn-ratio

1 or 2

SiO2

2.34.0

CaO

<1.0

Al2O3

2.25.4

0.050.13

0.030.12

Ti

0.040.11

0.0020.003

Coke

130170 g/kgore

mix.

Quartz

140240 g/kgore

mix.

Products
Mn-slag
MnO

4453

SiO2

3139

CaO

1.4

MgO

411

Al2O3

510

Fe

0.50.7

0.0040.010

0.20.5

Ti

0.100.19

0.0060.008

Hot metal
Fe

Balance

2.44.7

Si

0.05

Mn

3.25.0

0.110.46

0.0090.015

Ti

0.0015

0.0010

Table 4. Results of eight experiments on Mn-slag production via

German practice (chemical compositions in wt%).

2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.steel-research.de

FULL PAPER

Figure 2. SEM image and EDX analysis of a prereduced mass: virtual complete reduction of Fe and formation of a complex oxide of Mn, Si,
and some Fe (chemical compositions in wt%).

suitable. Performing desiliconization by solid oxidation

agents in several steps with intermediate slag removal may
help to reduce the amount of slag, because at higher silicon
contents a lower slag basicity and thus less CaO is required
(counter flow principle). Large additions of oxidizing agent
and burnt lime may seriously impair the economics of the
process, although the additional gain of manganese is
quite attractive.
The described process route can be installed in a
ferroalloy plant, but integration into an iron and steel
works could offer considerable synergies, the most obvious
one being introduction of the hot metal from Mn-slag
production into steelmaking. Furthermore, parts of the
plant equipment (e.g., agglomeration, rotary hearth
furnace, electric slag melting furnace) could also be used
for other purposes like recycling of steelmaking residues.
Recently, Min et al. took out a patent for a related
production route of FeMn with ultra low contents of
phosphorus and carbon via a reductive dephosphorization
of standard LC SiMn by a CaOCaF2-slag and its
subsequent desiliconization by a Mn-slag, which is
composed of slag from ordinary HC FeMn-smelting,
Mn-dust, and lime.[16]

3. Experimental
The individual process steps of the conceived production
route (Figure 1) have been experimentally studied on

2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 3. Appearance of products from Mn-slag production via

German practice (Fe/Mn-ratio 2 in feedstock).

steel research int. 85 (2014) No. 9999

FULL PAPER

www.steel-research.de

laboratory scale using commercial feedstock and process

conditions regarding temperature and time scale. Key
objectives have been to demonstrate the principal
feasibility of the concept, to identify and optimize the
key parameters of each step and to investigate the behavior
of detrimental impurities, particularly of phosphorus.
All experiments apart from prereduction trials were
conducted in a vacuum induction furnace (LeyboldHeraeus IS 1,5/II) equipped with a graphite susceptor
under 1000 mbar argon atmosphere. Temperatures were
measured using a thermocouple of type B. All specimens
were furnace cooled.
For production of Mn-slag according to the prementioned German practice, mixtures of iron ores and
manganese ores, quartz sand and a stoichiometric amount
of coke powder were prereduced in a capped stainless steel
container in a muffle furnace at 11008C for 4 h under
ambient atmosphere and were cooled in argon. The
prereduced mass was subsequently melted in the abovementioned induction furnace, applying crucibles cut from
commercial magnesia carbon bricks (RHI ANCARBON
CX93) and holding at 135014508C for 30 min.
Concerning the production of SiMn, various ground
Mn-slags were mixed with coke powder and quartz sand,
heated to 170017508C and held for 30 min in high-purity
graphite crucibles. In order to study the influence of the
feedstocks phosphorus content, coke and quartz sand
were replaced in a few cases by high-purity graphite and
silica powder, both being virtually free of phosphorus.
For desiliconization, a synthetic LC SiMn was produced
in accordance with the previous trials on SiMn-production
in order to provide a sufficient amount of feedstock with a
representative and constant chemical composition for all
subsequent desiliconization experiments. This synthetic
LC SiMn was equilibrated with the desiliconization slag at
15508C for 30 min in self-made CaO-crucibles, which were
prepared from commercial burnt lime (Schaefer Precal
30S) by uniaxial pressing and sintering at 17008C for 5 h.
Chemical analyses were conducted for all oxidic phases
via ICP-OES (Thermo IRIS Intrepid II XDL) and for all
metallic phases via GD-OES (LECO GDS850A), ICP-OES,
and CS combustion analysis (Eltra CS-2000).

4. Results and Discussion

4.1. Production of MnSlag
Solid state prereduction of agglomerated mixtures (feedstock in Table 4) yielded a virtual complete reduction of
iron oxides to metallic iron and a partial reduction of
manganese oxides to MnO in accordance with mass
balance and Figure 2. This is mostly in agreement with the
results of Ohler-Martins et al.,[17] who found a low
metallization degree of manganese at temperatures below
12008C for a similar experimental design. The small size of

steel research int. 85 (2014) No. 9999

Production of desiliconization slag

Feedstock
Ore mixture
Fe/Mn-ratio

SiO2

3.53.9

CaO

0.64.9

Al2O3

2.43.0

0.07

0.040.12

Ti

0.06

0.0030.03

Coke

136139 g/kgore

Quartz

3551 g/kgore

Alumina

101123 g/kgore

mix.

mix.
mix.

Products
Desilicon. slag
MnO

4855

SiO2

1314

CaO

18

MgO

27

Al2O3

2223

Fe

0.60.8

0.0020.008

0.20.3

Ti

0.110.13

0.0060.04

Hot metal
Fe

Balance

2.64.1

Si

0.01

Mn

8.213.6

0.180.34

0.0130.020

Ti

<0.001

<0.001

Table 5. Results of three experiments on production of

desiliconization slag (chemical compositions in wt%).

2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.steel-research.de

ratio in the feedstock, thus increasing the dilution of

phosphorus in the hot metal in order to lower its
phosphorus activity. However, a significant improvement
of dephosphorization was not observed.
In an additional series of experiments desiliconization
slag was produced as an oxidizing agent for posterior
desiliconization of SiMn. It should therefore have a low
SiO2-content and contained approx. 22 wt% Al2O3 and
13 wt% SiO2. The slags higher melting point necessitated
a holding temperature of about 15008C. Results are
summarized in Table 5. In comparison to the Mn-slags
lean of Al2O3, an even better dephosphorization of the slag
was achieved with phosphorus contents of 2080 ppmw in
the slag and 0.20.3 wt% in the metal. This is caused by the
lower oxygen potential as a consequence of the higher
temperature. The increase of temperature and MnOactivity caused a considerable reduction of manganese
yielding 814 wt% Mn in the metal, which makes a
limitation of carbon activity essential. The desiliconization
slags higher viscosity caused foaming, but phase separation was still sufficient.

4.2. Production of LC SiMn

Carbothermal reduction of the Mn-slag yielded metallic
SiMn and only very little slag as shown in Figure 4. An
overview of feedstock and products is given in Table 6. In
case of coke and quartz sand in the feedstock, the LC SiMn
contained 130190 ppmw phosphorus, which is substantial lower in comparison to conventional SiMn grades. By
using high-purity graphite and silica, phosphorus could
even be decreased to 80 ppmw. Hence, the SiMns
phosphorus content is mainly controlled by the supplementary introduction of phosphorus via coke and quartz
sand being fed to the process along with the previously
dephosphorized Mn-slag. In order to minimize the
required addition of quartz sand, a Mn-slag with a highest
possible SiO2-content should be utilized.
The yield of phosphorus into the SiMn did not exceed
90%. It is known from the literature that some evaporation
losses of approx. 1020% occur for phosphorus in

Figure 4. Appearance of products from LC SiMn production: nearly no oxides are left.

2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

steel research int. 85 (2014) No. 9999

FULL PAPER

the metallic particles and their fine coalescence with the

non-metallic phases make a physical processing of the
prereduced mass appear unpromising.
In subsequent melting of the prereduced masses, the
obtained slags showed a relatively high fluidity at 1350
14508C resulting in a good phase separation of metal and
slag as shown in Figure 3. The chemical analyses of metal
and slag are given in Table 4. It was succeeded to
selectively remove the bulk of iron and phosphorus into
the hot metal, thus producing a MnOSiO2 based Mn-slag
with sufficient low phosphorus contents appropriate for
subsequent reduction to SiMn.
The extensive reduction of phosphorus from slag to
metal is caused by its high activity in the quite acidic slag as
well as by the systems low oxygen potential at the
prevailing temperature and carbon activity. Although the
latter approaches unity according to the metals high
carbon contents, manganese was only slightly reduced to
the metal. This is in accordance with the results of Qiang
et al.,[18] who applied similar process conditions. The
limited Mn-reduction results from the comparatively high
thermodynamic stability of MnO as well as the moderate
temperatures and is further restricted by the low MnOactivity of approx. 0.2 (referred to pure solid MnO)[19] due
to moderate slag basicity. Hence, by adjusting the
temperature high enough to ensure sufficient fluidity of
metal and slag, but low enough to limit Mn-reduction,
tolerably low manganese losses to the metal can be
achieved even under carbon saturation. If higher temperatures are required due to increased liquidus temperature
of the slag as in case of desiliconization slags, carbon
activity has to be decreased by utilizing carbon free
refractories such as silica (at least in laboratory experiments due to the high ratio of surface to volume). The Mnslag absorbed some MgO from the crucible and sulfur from
the coke. In contrast to phosphorus, sulfur mainly
remained in the slag as its reduction to the metal is
inhibited by the low oxygen activity in the metal and the
high sulfide capacity of the slag. The selective reduction of
boron and titanium is prohibited by the high thermodynamic stability of their oxides. An attempt was made to
improve the dephosphorization by doubling the Fe/Mn-

FULL PAPER

www.steel-research.de

LC SiMn production
Feedstock
Mn-slag
MnO

4351

SiO2

3639

CaO

1.21.4

MgO

4.26.8

4.3. Desiliconization

Al2O3

4.74.9

Fe

0.50.7

0.007

0.250.50

Ti

0.130.16

0.006

The reaction between synthetic LC SiMn and desiliconization slag resulted in a good phase separation. Table 7
compiles the experimental results. A tailored LC SiMn
suitable for high manganese steelmaking could be
obtained. The silicon in the metal was oxidized down to
approx. 510 wt% while MnO remaining in the final slag
was low at 510 wt%. Ratios of Mn/Si in the range of 916
were achieved. The measured metal-slag equilibrium of
manganese and silicon according to Reaction (1) is in good
agreement with the values of Tuset[23] due to similar slag
systems and basicity, as can be seen from the compilation
of literature data in Figure 5.

Coke (0.038 P)

230270 g/kgMn-slag

Quartz (0.026 P)

70120 g/kgMn-slag

Products

Si 2MnO@SiO2 2Mn

LC SiMn
Mn

5970

Si

2837

Fe

0.751.8

(0.070.61)

0.0130.019 (0.008)

0.0020.011

Ti

0.190.33

0.0030.008

Ca

0.030.48

Mg

0.0010.12

Al

0.030.80

Yield

450550 g/kgMn-slag

Table 6. Results of five experiments on LC SiMn production

(chemical compositions in wt%).

commercial SiMn production.[20] A limited additional

refining effect is therefore achieved.
Corresponding to its high silicon contents, the produced SiMn was low in carbon, although some of the
measured carbon contents notably exceed the equilibrium
values of carbon saturation due to incorporated SiC, which
could not be removed during sample preparation. Favored
by the systems low oxygen potential, sulfur in the SiMn
was low despite its high content in the feedstock. It was

removed by evaporation since an enrichment of sulfur was

measured in the furnace dust. For boron and titanium no
refining effect could be observed. The few slag mainly
consisted of Al2O3, SiO2, CaO, and MgO, but its small
quantity prohibited an accurate chemical analysis. The
overall metal yield was 450550 g/kgMn-slag with the main
mass loss resulting from oxygen removal.

steel research int. 85 (2014) No. 9999

The equilibrium is mainly influenced by the basicity, as

a rising basicity increases the MnO-activity and decreases
the SiO2-acitvity. In the present work, the basicity reached
high values up to %CaO%MgO
1:9 due to CaO saturation
%SiO2
of the slag resulting from the utilization of calcia crucibles.
Thus an almost optimal case of desiliconization was
investigated from the viewpoint of thermodynamics.
Temperatures between 1400 and 16008C have no significant effect on the metal-slag equilibrium of manganese
and silicon,[14,21,22] which is in agreement with the minor
temperature dependence of the standard Gibbs energy of
Reaction (1) in this temperature range. The same applies to
iron in contents up to 20 wt%.
Most phosphorus from the feedstock ended up in the
tailored LC SiMn, which agrees with the data from Min
et al.[16] Nevertheless, its final phosphorus content of 140
160 ppmw is low enough for high manganese steelmaking.
Virtually all iron was reduced to the metal phase, while the
bulk of titanium was oxidized to the slag. The tailored LC
SiMn picked up some carbon probably originating from
the reaction of the applied carbon susceptor with residual
oxygen in the furnace atmosphere. Sulfur predominantly
remained in the slag, while boron was distributed rather
evenly between both phases.

5. Conclusions
The industrial production of high manganese steels with
approx. 1030 wt% Mn makes high demands on the

2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.steel-research.de

FULL PAPER

Desiliconization
Feedstock

Products

Synthetic LC SiMn

Tailored LC SiMn

Mn

68.5

Mn

86.990.6

Si

28.7

Si

5.59.6

Fe

0.92

Fe

1.92.4

0.04

0.130.29

0.012

0.0160.017

0.005

0.0070.010

Ti

0.23

Ti

0.0050.019

0.009

0.0070.009

Ca

0.007

Ca

0.020.09

Mg

0.0002

Mg

< 0.01

Al

0.09

Al

0.0030.03

Yield

1.31.5 kg/kgSyn.

Desiliconization slag
MnO

54.9

SiO2

13.0

MnO

5.310.1

CaO

1.3

SiO2

24.826.8

MgO

3.6

CaO

44.146.8

Al2O3

22.2

MgO

2.83.0

Fe

0.6

Al2O3

16.418.0

0.008

Fe

0.020.03

0.18

0.0010.002

Ti

0.13

0.130.16

0.007

Ti

0.210.23

Quantity

1.62.5 kg/kgSyn.

SiMn

0.0020.008

Burnt lime

0.50.9 kg/kgSyn.

SiMn

(CaO MgO)/SiO2

1.71.9

SiMn

Slag

Table 7. Results of four experiments on desiliconization (chemical compositions in wt%).

utilized Mn-bearing alloying agents in terms of chemical

purity and cost-efficiency. Among conventional Mnbearing alloying agents, only electrolytic manganese
metal features an adequate purity, which on the
downside suffers from high prices and few suppliers
as well as from hydrogen and selenium contamination
in some cases.
A modified production route for special grades of
silicomanganese tailored for high manganese steelmaking has been conceived. Starting from various mixtures
of Mn- and Fe-bearing ores and residuals, its key feature
is the pyrometallurgical winning of a manganese slag

2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

of MnOSiO2-type, which is low in phosphorus. This

is achieved via removal of the bulk of iron and
phosphorus by selective carbothermal solid-state reduction and phase separation by melting. The process
step may be operated by three different practices,
principally differing from each other in the metal phase,
which is obtained as by-product. Thus produced Mnslag serves as high-grade feedstock for subsequent
silicomanganese production by conventional means.
Depending on the desired carbon content of the final
product, a high-grade silicomanganese with adjusted
Mn/Si-ratio is produced either directly from the Mn-slag

steel research int. 85 (2014) No. 9999

FULL PAPER

www.steel-research.de

Figure 5. Compilation of Mn/Si equilibrium for desiliconization.

or indirectly via a low carbon silicomanganese being

finally desiliconized.
Lab-scale experiments in accordance with theoretical
considerations and literature data prove the conceived
process route to be technically feasible and expedient. It
provides tailored SiMn grades of adequate chemical
composition for high manganese steelmaking. Economic feasibility, however, has yet to be proven. The plant
used for Mn-slag production, e.g., consisting of a rotary
hearth furnace for prereduction and an electric slag
melting furnace for metal-slag separation, could simultaneously be used for recycling dusts and slags. In the
end, the tailored SiMn grades would be in economical
competition with commercial electrolytic manganese
metal.

Acknowledgment
This work has been partly funded by the German Federal
Ministry of Education and Research under grant No.
033R007B.

10

steel research int. 85 (2014) No. 9999

Received: May 1, 2014

Keywords: high manganese steels; silicomanganese;

manganese; ferroalloys

References
[1] G. Frommeyer, Stahl Eisen 2007, 127, 67.
[2] M. R. Aboutalebi, M. Isac, R. I. L. Guthrie, Steel Res.
Int. 2004, 75, 366.
[3] Z. Georgeou, J. Schottler, D. Rohrberg, K.-H. Spitzer,
A. Newirkowez, R. Nystom, Stahl Eisen 2012, 132, 29.
[4] C. F. Redeker, H.-J. Renner, J. Schottler, K.-H. Spitzer,
D. Rohrberg, A. Newirkowez, S. Acharya, R. Nystrom,
P. Hahlin, Res. Fund Coal Steel No. RFSR-CT-200300016, 2008.
[5] Z. Georgeou, C. F. Redeker, J. Schottler, R.-H.
Gronebaum, A. Redenius, J. Kroos, A. Newirkowez, D.
Rohrberg, J. Wendelstorf, K.-H. Spitzer, R. Nystrom,
Res. Fund Coal Steel No. RFSR-CT-2006-00005, 2010.

2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.steel-research.de

2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

[15] R. N. McClure, Proc. Electric Furnace Conf., Metall.

Soc. AIME 1961, 19, 307.
[16] D.-S. Min, C.-S. Park, Y.-E. Lee, H.-C. Cho, K.-J. Lee,
S.-H. Hong, Patent US8268036B2 2012.
[17] K. Ohler-Martins, D. Senk, Steel Res. Int. 2008, 79, 811.
[18] Z. Qiang, N. Shun-ming, C. Wen, T. Sanchuan, L.
Zhaojia, W. Hong-qiang, in 3rd Int. Symp. HighTemperature Metall. Proc. (Eds: T. Jiang, J.-Y. Hwang,
P. Masset, O. Yucel, R. Padilla, G. Zhou), John Wiley &
Sons 2012, 515.
ttenleute (ed.), Slag Atlas,
[19] Verein Deutscher Eisenhu
Verlag Stahleisen 1995.
[20] A. L. Groshkova, L. A. Polulyakh, A. Y. Travyanov, V. Y.
Dashevkii, Y. S. Yusfin, Steel Transl. 2007, 37, 904.
[21] G. J. W. Kor, Metall. Trans. B 1979, 10B, 367.
[22] E. T. Turkdogan, Can. Metall. Quart. 2001, 40, 255.
[23] J. K. Tuset, Proc. 69th Steelmaking Conf., Iron Steel
Soc. 1986, 1, 59.
[24] N. A. Barcza, J. S. Afr. Inst. Min. Metall. 1979, 79, 269.
[25] N. A. Barcza, D. P. OShaughnessy, Can. Metall.
Quart. 1981, 20, 285.

steel research int. 85 (2014) No. 9999

11

FULL PAPER

[6] J. A. Vazquez Monroy, Dephosphorization of liquid

ferromanganese and high manganese steels by
utilization of various slag mixtures (in German),
dissertation, RWTH Aachen 2009.
[7] G. Hils, A. Newirkowez, D. Rohrberg, K.-H. Spitzer, U.
Grethe, J. Kroos, 3rd CSM-VDEh Metall. Semin. 2011.
[8] E. Beppler, R. Fichte, A. Berger, H. Weber, in
Ullmanns Encyklopadie der technischen Chemie (Ed:
E. Bartholome), Verlag Chemie, 1978, 16, 425.
[9] V. P. Elyutin, Y. A. Pavlov, B. E. Lewin, E. M. Alekseev,
Israel Progr. Sci. Trans. 1962.
[10] P. Ischebeck, J. Willems, Arch. Eisenhuettenwes. 1952,
23, 1.
ttenleute (ed.): New paths
[11] Verein Deutscher Eisenhu
for manganese concentration in hot metal
production (in German), report no. 60, 1944.
[12] G. Volkert, Arch. Eisenhuettenwes. 1948, 19, 1.
[13] M. M. Gasik, Metallurgija i koksochimija 1983, 19, 28.
[14] S. E. Olsen, M. Tangstad, T. Lindstad, Prod.
Manganese Ferroalloys, Tapir 2007.