High Temp. Mater. Proc.
2016; 35(7): 635–641
Pei-Xian Chen*, Shao-Jun Chu and Guo-Hua Zhang
A New Method to Produce Ni–Cr Ferroalloy Used
for Stainless Steel Production
DOI 10.1515/htmp-2015-0054
Received March 9, 2015; accepted June 23, 2015
Abstract: A new electrosilicothermic method has been
proposed in the present paper to produce Ni–Cr ferroalloy,
which can be used for the production of 300 series stain-
less steel. Based on this new process, the Ni–Si ferroalloy
is first produced as the intermediate alloy, and then the
desiliconization process of Ni–Si ferroalloy melt with chro-
mium concentrate is carried out to generate Ni–Cr ferroal-
loy. The silicon content in the Ni–Si ferroalloy produced in
the submerged arc furnace should be more than 15 mass%
(for the propose of reducing dephosphorization), in order
to make sure the phosphorus content in the subsequently
produced Ni–Cr ferroalloy is less than 0.03 mass%. A high
utilization ratio of Si and a high recovery ratio of Cr can be
obtained after the desiliconization reaction between Ni–Si
ferroalloy and chromium concentrate in the electric arc
furnace (EAF)–shaking ladle (SL) process.
Keywords: Ni–Cr ferroalloy, stainless steel, electrosili-
cothermic metallurgy, dephosphorization, desiliconization
Introduction
The growth rate of stainless steel consumption is the
highest one among all materials in the world today
(ISSF, 2009). Unfortunately, its further growth will be
restricted by the resource supply and production cost.
The consumption of nickel and chromium ferroalloys
accounts for most of the cost of stainless steel produc-
tion: for example, 62% and 16% for nickel and chromium
in the production of stainless steel slabs (not including
*Corresponding author: Pei-Xian Chen, School of Metallurgical and
Ecological Engineering, University of Science and Technology
Beijing, Xueyuan Road 30, Haidian District, Beijing 10083,
P.R. China, E-mail: flywincpx@126.com
Shao-Jun Chu, School of Metallurgical and Ecological Engineering,
University of Science and Technology Beijing, Xueyuan Road 30,
Haidian District, Beijing 10083, P.R. China,
E-mail: chushaojun@metall.ustb.edu.cn
Guo-Hua Zhang, State Key Laboratory of Advanced Metallurgy,
University of Science and Technology Beijing, Xueyuan Road 30,
Haidian District, Beijing 10083, P.R. China,
E-mail: ghzhang_ustb@163.com
overhead) [1], respectively. It is possible to make a profit-
able stainless steel production process by reducing nickel
and chromium addition. Currently, there are two methods
to produce Ni–Cr stainless steel: using ferronickel instead
of nickel metal [2] and directly reducing chromium ore
fines by carbon in a smelting reduction–kawasaki com-
bined blown converter instead of using ferrochromium
alloy [3].
However, there are some problems in ferronickel
production process. Ferronickel is a ferroalloy typically
containing about 70–90% iron and 10–30% nickel. It is
always produced by the rotary kiln-electric furnace
(RKEF) smelting process from lateritic nickel ores. But in
China, submerged arc furnace (SAF) is the most widely
used furnace to produce ferronickel. Generally, to meet
the requirement from the traditional stainless steel
production, the ferronickel alloy is expected to be
produced with a low content of silicon so that it is
expected that the ores containing low silica content or
the reductant is less used. However, lateritic nickel ore is
always with a high silica content so that the quantity of
coke has to be controlled in a low level [4, 5], which leads
to the obvious increase of resistance of furnace burden.
Consequently, the operation mode with a low current and
high voltage for SAF has to be required in ferronickel
production process. It is very different from the tradi-
tional operation mode for SAF, which is used to produce
ferromanganese, ferrosilicon or ferrochromium alloy.
Another problem is to increase the service life of furnace
lining. Carbon-based lining was always adopted in the
SAF when producing silicomanganese and ferromanga-
nese alloys. However, it cannot be used in the production
of ferronickel alloy because a large amount of carbon
could be quickly dissolved into ferroalloy with low silicon
content. Therefore, if lateritic nickel ore is used to pro-
duce ferronickel with high silicon content in the tradi-
tionally SAF with carbon-based lining, the problems
mentioned above can be avoided.
In addition, utilization of chromium concentrate is one
of the most important problems in ferrochromium produc-
tion process. Over 80% of the world’s known exploitable
chromite resources are located in South Africa, in which
30% is lumpy ore and 70% is fine or friable ore [6].
Usually, chromium concentrate is pelletized in pelletizing
636 P.-X. Chen et al.: A New Method to Produce Ni–Cr Ferroalloy
drum firstly and then charged into a sintering furnace to
enhance its strength to bear the transport and impact,
which causes the increases in the cost and the energy
consumption for ferrochromium production. Hence, the
beneficial way for stainless steel production is to use
chromite concentrate directly instead of ferrochromium
alloy.
In view of the problems involved in the traditional
production processes of ferronickel and ferrochromium
alloys [6], a new method is introduced to produce the
Ni–Cr ferroalloy in this paper, which can provide new
sources of Ni and Cr for Ni–Cr stainless steel production
instead of ferronickel and ferrochromium alloys.
Metallurgical fundamental
The new method is based on the silicothermic reduction
reaction, which is always called as electrosilicothermic
method in the industry of ferroalloys. Actually, it has
been widely applied to produce ferromanganese and fer-
rochromium alloys with the low/medium carbon content
in the ferroalloy industry [7]. However, there is no report
in the literatures about producing stainless steel with this
method. The reaction principle of electrosilicothermic
method is always expressed as eq. (1) and it can be
expressed as eq. (2) when it is used to produce Ni–Cr
ferroalloy:
½Si þ ðMeOÞ ! ½Me þ ½SiO2  ð1Þ
3y½SiFe þ 2yðCr2 O3 Þchromium concentrate þ 3xðCaOÞlime
¼ 4y½Cralloy þ 3ðxCaO  ySiO2 Þslag
ð2Þ
If assuming that x ¼ 2, y ¼ 1 in eq. (2), the change of
standard Gibbs free energy can be calculated as shown in
eq. (3) by the data from literatures [8, 9]. In the temperature
range of 1,673–1,873 K, the change of standard Gibbs
free energy is –611.186 to –614.634 kJ · mol−1, which
indicates that reaction (3) can spontaneously happen
in the standard state from the view point of
Table 1: Chemical compositions of 300 series stainless steel in duplex and triplex processes.
Process Name C (%) P (%) S (%)
Duplex Primary steel < <. <.
Refined steel <. <. <.
Triplex Primary steel <. <. – <.
Refined steel <. <. – .
thermodynamics. Thereby, in the actual case, it can
take place much more easily because of the high
silicon content and low chromium content in the initial
ferroalloy melt:
3½Si1% þ 2Cr2 O3ðsÞ þ 6CaOðsÞ ¼ 4½Cr1% þ 3Ca2 SiO4ðlÞ

ΔG ðT ¼ 1; 6731; 873 KÞ ¼ 582:343  0:017T kJ  mol1
ð3Þ
In the new process, the ferronickel alloy containing high
silicon, which is also named as nickel–silicon ferroalloy,
is designed as the source of silicon. Then Cr2O3 in the
chromium concentrate is reduced by nickel–silicon fer-
roalloy to produce Ni–Cr ferroalloy.
Therefore, a process for producing 300 series stain-
less steel with this method can be proposed and its flow
diagram is shown in Figure 1. The nickel–silicon ferroal-
loy is produced by sintering-SAF process and then the
obtained molten metal will react with chromium concen-
trates in electric arc furnace (EAF) and shaking ladle (SL)
to get primary stainless steel metal which can be placed
in argon oxygen decarburization (AOD)/vacuum oxygen
decarburization (VOD) vessel for refining finally. The
main aim of electrosilicothermic process presented in
this paper is to get the primary stainless steel which is
similar to that in the traditional stainless steel production
process. Table 1 shows the typical composition of
Figure 1: Flow diagram of electrosilicothermic process for 300 series
stainless steel production.
Si (%) Mn (%) Cr (%) Ni (%)
<. .  .
. . . .
.  .
. . .
 P.-X. Chen et al.: A New Method to Produce Ni–Cr Ferroalloy 637

300 series stainless steel required in the traditionally
duplex and triplex stainless steel production processes.
As shown in Table 1, except for Fe, Cr and Ni, attention
should also be paid on phosphorus and silicon in stain-
less steel production. It means that if phosphors and
silicon can be controlled in the new electrosilicothermic
process, it is possible that the primary 300 series stain-
less steel is produced by this new process.
Experimental
In order to determine whether it is possible to produce
appropriate Ni–Cr ferroalloy by the new method or not,
some technological experiments have been done in a
pilot-scale plant, including dephosphorization (de-P)
and desiliconization (de-Si) experiments in nickel–silicon
ferroalloy melt.
Apparatus and materials
Experimental works were carried out in the medium fre-
quency induction furnace. The information of corresponding
raw materials is shown in Table 2. The ferronickel alloy
extracted from lateritic nickel ore in SAF was taken from
one plant in China.
Process
In the de-P experiment, the nickel–silicon ferroalloy with
about 0.04–0.06 mass% P and about 5–30 mass% Si was
smelted in MgO crucible by using ferronickel alloy, metal-
lic silicon and ferrophosphorus as the raw materials.
Then alloy samples were taken by quartz tube before
adding the de-P agent. After reacting for 10 min, another
alloy sample was taken again. The weight ratio of de-P
agent to metal was about 1:10. Two kinds of de-P agent
were used: the one for precipitation de-P contains about
50% calcium-silicon alloy, 25% lime and 25% fluorite; the
other one for interface de-P contains about 60% lime and
40% fluorite.
In the de-Si experiment, the nickel–silicon ferroal-
loy after de-P was first melted in the induction furnace,
and then the mixture of chromium concentrate (50–60
mass%) and lime (40–50 mass%) was added in the sur-
face of alloy melt. The samples of slag and metal were
taken after reacting for about 25 min. According to the
process shown in Figure 1, de-Si process was divided
into two steps. The first step was pre-de-Si process, in

Table 2: Raw materials used in de-P and de-Si experiments.

Experiment Raw material Chemical composition Size/weight

De-P Fe–Ni alloy Ratio of Ni to Fe is about : (Ni: . mass%), Si: . mass%, About  kg
P: . mass%, C: . mass%, Cr: .–. mass%
Metallic silicon Si: . mass%, P: . mass%
Ferrophosphorus P: . mass%, Fe: .%
Lime CaO: . mass%, P <. mass%, < mesh
SiO: . mass%
Fluorite CaF: . mass%, < mesh
SiO <. mass%, P <. mass%
Calcium–silicon alloy Si: . mass%, Ca: . mass%, < mesh
Fe: . mass%, P: . mass%

De-Si Ni–Si ferroalloy Ni: about  mass%, About  kg

Si: about  mass%,
P < . mass%, C <. mass%,
S <. mass%
Chromium concentrate CrO: . mass%,
FeO: . mass%,
CaO: . mass%,
SiO: . mass%,
P <. mass%, S <. mass%
Lime CaO >  mass%, P < . mass%, < mesh
S <. mass%, SiO: . mass%
638 P.-X. Chen et al.: A New Method to Produce Ni–Cr Ferroalloy

which the silicon content of nickel–silicon ferroalloy
was decreased from 25 mass% to about 10–19 mass%;
the second step was the final de-Si process, in which the
silicon content was decreased from about 10 mass% to
less than 1 mass%.
Results and discussion
De-P experiment in Ni–Si ferroalloy melt
Since an important evaluation criterion for primary stain-
less steel liquid is its phosphorus content, low phos-
phorus content is required for the Ni–Cr ferroalloy.
In the electrosilicothermic process, if the lime is used
with the phosphorus content less than 0.01 mass%, the
phosphorus content of Ni–Cr ferroalloy will be deter-
mined by that of the nickel–silicon ferroalloy, with the
consideration of the lower than 0.01 mass% phosphorus
in the chromium concentrates [10]. Under this condition,
nickel–silicon ferroalloy with the phosphorus content
less than 0.03 mass% can be used for 300 series stainless
steel production.
Usually, the phosphorus content of nickel–silicon
ferroalloy is controlled by employing raw materials
with a low phosphorus content [11]. However, the case
can happen that the phosphorus content is still higher
than 0.035 mass%. In this case, it is necessary to adopt
a de-P process for nickel–silicon ferroalloy as shown in
Figure 1. When silicon content in iron is between 5 and
30 mass%, the melt is under the condition of strong
reduction and it is possible to adopt reductive de-P
method [12, 13]. The experimental results of reductive
dephosphorizations of different nickel–silicon ferroalloy
melts are shown in Table 3 and Figure 2. It should be
mentioned that the Cr content of Ni–Cr ferroalloy pro-
duced by electrosilicothermic method might be higher
than that of 300 series stainless steel or other Ni–Cr
stainless steel. In this case, some low phosphorus pig
iron and electrolytic nickel can be added in the stainless
steel production process.
One of the important influence factors for the reduc-
tive de-P is silicon content of nickel–silicon ferroalloy,
and the de-P efficiency (defined as the ratio of
the change of phosphorus content to its initial value)
is increased with the increase of the silicon content.
It was found that precipitation de-P efficiency was larger
than 30% when silicon content of nickel–silicon ferroal-
loy was higher than 15 mass%. However, for the inter-
face de-P, only when the silicon content was more
than 25 mass%, the de-P efficiency can reach the same
value of precipitation de-P when silicon content was
15 mass%. In addition, because the quantity of de-P
agent in no. 13 experiment was one time more than
that of other experiments, the de-P efficiency of this

Table 3: The experimental results of two kinds of de-P experiments.

Method No. De-P

Before de-P After de-P
efficiency (%)
Fex Ni Si P Fe Ni Si P

Precipitation de-P  . . . . . . . . .
 . . . . . . . . 
 . . . . . . . . 
 . . . . . . . . 
 . . . . . . . . 
 . . . . . . . . 
Interface de-P  . . . . . . . . .
 . . . . . . . . .
 . . . . . . . . 
 . . . . . . . . 
a . . . . . . . . 
 . . . . . . . . 
b . . . . . . . . 
 . . . . . . . . 

Note: aThe initial content of sulfur in the nickel–silicon alloy is about 0.02 mass%, and the initial content of sulfur in nickel–silicon alloy in
other de-P experiments is less than 0.01 mass%.
b
The weight ratio of the de-P agent to metal is 1:5.

80%
Precipitation dephosphorization
70% Interface dephosphorization
Dephosphorization efficiency
60%
50%
40%
30%
20%
10%
0%
5 10 15
Silicon content (mass%)
Figure 2: Relationship between de-P efficiency and silicon content
of nickel–silicon ferroalloy with different reductive de-P
experiments.
experiment was much higher. It means that it is possibly
an effective way to increase the de-P efficiency by
increasing the quantity of de-P agent when the silicon
content of alloy melt is constant. However, the large
amount of slag used in the production process is also
inappropriate. Therefore, if the silicon content of
nickel–silicon ferroalloy should be designed to be
higher than 15 mass%, then the phosphorus in the
alloy can be reduced by reductive de-P process to meet
the requirement of stainless steel production. Li et al. [4]
have proved that it was possible to produce the ferro-
nickel alloy containing about 18 mass% silicon content
with the sintering-SAF process.
Another important influence factor for reductive de-
P is the initial sulfur content of the nickel–silicon alloy.
Compared with no. 10 experiment, the de-P efficiency of
no. 11 was decreased by a half because of its high initial
sulfur content. The reason for this is that the slag with
CaO and CaF2 is also a good desulfurization agent for
Ni–Si ferroalloy. Therefore, the sulfur content of nickel–
silicon content must be controlled strictly before reduc-
tive de-P or the quantity of de-P agent should be
increased during the de-P process in the case of high
sulfur content.
As shown in Table 3, it is an effective method to
decrease the phosphorus in nickel–silicon ferroalloy by
the reductive de-P method. However, this method can
also lead to the formation of Ca3P2 in slag, which is
noxious and difficult to be handled. Fortunately, an effec-
tive method to deal with Ca3P2-bearing slag has been
developed elsewhere [14, 15].
P.-X. Chen et al.: A New Method to Produce Ni–Cr Ferroalloy 639
De-Si of Ni–Si Ferroalloy reacted
with chromium concentrate
After de-Si process, the silicon content should be less
than 1 mass%. Meanwhile, the recovery ratio of Cr and
utilization ratio of Si are very important during the de-Si
process. There are two processes for de-Si in the ferroal-
loy industry: one-step process (EAF process) and two-step
process (EAF–SL process). One-step process means that
the silicon content of nickel–silicon ferroalloy is reduced
for one time and the silicothermic reaction just occurs in
the EAF. Two-step process refers to that the silicon con-
20 25 30 tent is reduced for two times in EAF and SL, respectively.
If the material balance of the two processes can be cal-
culated theoretically with the principles of mass conser-
vation and the chemical equilibrium of de-Si reaction
between Ni–Si ferroalloy and chromium concentrate,
then the recovery ratio of Cr and utilization ratio of Si
can be calculated and compared.
The reaction occurring in the de-Si process is shown in
eq. (4), with the equilibrium constant described in eq. (5):
3Si þ 2ðCr2 O3 Þ ¼ 4½Cr þ 3ðSiO2 Þ ð4Þ
a4Cr  a3SiO2
K¼ ð5Þ
a2Cr2 O3  a3Si
where K is equilibrium constant and ai is the activity of i.
So activity of silicon in molten Ni–Cr ferroalloy can
be expressed as
 2=3
a2Cr 1
aSi ¼  aSiO2  ð6Þ
aCr2 O3 K
Therefore, the silicon content of Ni–Cr ferroalloy may be
decided by the basicity of slag, the distribution ratio of Cr
in metal and slag, ignoring the temperature dependence
of K. It means that the silicon content of Ni–Cr ferroalloy
after the reaction reached chemical equilibrium can be
expressed as in eq. (7):
 
½Cr2
½Si ¼ f ; R ð7Þ
ðCr2 O3 Þ
where R ¼ ðCaOÞ=ðSiO2 Þ.
However, the chemical equilibrium experiment was
not carried out in this paper. In the practical production
process, the de-Si reaction also cannot reach real chemical
equilibrium, so that the relationship among silicon con-
tent, R and ½Cr2 =ðCr2 O3 Þ obtained from the present tech-
nological experiments is enough to guide the de-Si in the
stainless steel production process proposed in this paper.
640 P.-X. Chen et al.: A New Method to Produce Ni–Cr Ferroalloy

Table 4: Compositions of metal and slag in the de-Si experiments of Ni–Si ferroalloy.

Process Metal (mass%) Slag (mass%)

Fe Si Ni Cr P S CrO CaO SiO MgO AlO FeO R

Pre-de-Si . . . . . <. . . . . . . .
. . . . . <. . . . . . . .
. . . . . <. . . . . . . .
. . . . . <. . . . . . . .
. . . . . <. . . . . . . .
Final de-Si . . . . . . . . . . . . .
. . . . . . . . . . . . .
. . . . . <. . . . . . . .

The results of de-Si experiments are shown in Table 4, and basicity is from 1.3 to 1.6, the recovery ratio of Cr is
the relationship among silicon content, R and ½Cr2 =ðCr2 O3 Þ controlled at the level of 85.32–93.48%; while, when it
after de-Si is expressed in eqs (8) and (9). is produced by EAF–SL process, the silicon content in the
When silicon content is higher than 10 mass%, the alloy must be within 15.70–16.30% after pre-de-Si to
relationship is result in a recovery ratio of Cr to be 93.95–97.53%. In
other words, the EAF–SL process can increase the recov-
½Cr%2
½Si% ¼ 60:703  0:030  29:616R ð8Þ ery ratio of Cr although the corresponding equipment
ðCr2 O3 %Þ investment also increases.
When silicon content is less than 10 mass%, the In addition, Table 4 shows that the phosphorus and
relationship is sulfur of alloy were not increased obviously after de-Si.
Figure 3 shows the change of alloy composition during
½Cr%2
½Si% ¼ 4:967  0:003  2:587R ð9Þ the present process. The final product after electrosili-
ðCr2 O3 %Þ
cothermic process contains about 30 mass% Cr, which
According to the mass conservation and eqs (8) and is higher than the requirement for 300 series stainless
(9), the comparisons of the EAF and EAF–SL processes steel liquid (shown in Figure 1). It can be used as the
for de-Si are calculated and shown in Table 5 [16]. When master alloy of 300 series stainless steel with the addi-
Ni–Cr ferroalloy is produced in EAF process and the slag tions of a certain amount of nickel plate and iron.

Table 5: Calculation of material balance for EAF and EAF–SL processes.

Raw materials for calculation

Ni–Si–Fe Fe Si Ni Cr P S
.% .% .% .% .% .%
Cr concentrate CrO FeO SiO CaO MgO AlO
.% .% .% .% .% .%
Lime CaO SiO AlO MgO FeO P
.% .% .% .% .% .%

Process Ni–Cr ferroalloy Disposal slag Utilization ratio of Si Recovery ratio of Cr

Ni Cr Si CrO R

EAF process .% .% .% .% . .% .%

.% .% .% .% . .% .%
.% .% .% .% . .% .%
.% .% .% .% . .% .%
EAF–SL process .% .% .% .% . .% .%
.% .% .% .% . .% .%
 P.-X. Chen et al.: A New Method to Produce Ni–Cr Ferroalloy 641

production) with a low phosphorus content. In addition,

Ferronickel alloy
(Ni: 8.75%, Cr: 2.51%, Si: 2.43%, P: 0.023%, S < 0.01%) to get a high recovery ratio of Cr and a high utilization
Add ferrophosphorus and metal silicon
ratio of Si, the de-Si process can be optimized by using
EAF–SL process.
Ni–Si ferroalloy with high P content
(Ni: 6.68%, Cr: 1.87%, Si: 24.79%, P: 0.059%, S < 0.01%)
Funding: The authors gratefully acknowledge the finan-
Precipitation de-P Add SiCa alloy, lime and fluorite cial support from National Natural Science Foundation of
China (no. 51274030) for this project.
Ni–Si ferroalloy after de-P
(Ni: 6.59%, Cr: 1.86%, Si: 25.57%, P: 0.030%, S < 0.01%, C: 0.11%)

De-Si process Add chromium concentrate and lime

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