Available online at www.sciencedirect.

com

*·## ScienceDirect
JOURNAL OF IRON AND STEEL RESEARCH, INTERNATIONAL. 2013, 20(1) : 26-33

Industrial Application of Desulfurization Using Low

Basicity Refining Slag in Tire Cord Steel
C H E N Shu-hao1·2, W A N G Xin-hua2, H E Xiao-fei 2 , W A N G Wan-jun2, J I A N G Min 2
( 1 . School of Metallurgical Science and Engineering, Central South University, Changsha 410083,
H u n a n , China; 2. School of Metallurgical and Ecological Engineering, University of Science and
Technology Beijing, Beijing 100083, China)

Abstract: Desulfurization performance with low binary basicity refining slag in 72 grade tire cord steel was calculated
using FactSage and it is found that sulfur content in steel decreases with the increase of basicity of slag, MgO content
in slag and slag/steel ratio while sulfur partition ratio between slag and steel increases gradually with the increase of
basicity of slag as well as MgO content. Experiments were carried out and the results are of great agreements with
theoretical calculation. Then industrial application tests were performed in a domestic plant and good results were achieved.
Sulfur content in steel decreases gradually during refining process, as a result, sulfur content in the billets is con­
trolled in the range of 0. 007 1% — 0. 008 1%. Sulfur content in steel refined with slag basicity of 1. 21 is lower than
that of 1. 0 2 , while the plasticity of oxide compound inclusions is a little better controlled in low basicity heats. Using refi­
ning slag with b a s i c i t y o f l . O —1.2 and MgO content of 5 % — 1 0 % and reducing the slag takeover of LD are favorable
for improving the desulfurization performance and the plasticity of inclusions during the industrial production.
Key words: FactSage; desulfurization behavior; low basicity; refining slag; sulfur partition ratio; sulfur content

A s an impurity element b r o u g h t in steel from performed during t h e hot metal p r e t r e a t m e n t and

steelmaking raw m a t e r i a l s , sulfur would initiate hot
s h o r t n e s s p h e n o m e n o n in steel products at high t e m ­
p e r a t u r e so it is a harmful element for most steel
grades'-1-1. Sulfur and manganese would combine to
form manganese sulfide in high manganese content
s t e e l s , which is a plastic inclusion expanding along
the rolling direction in hot rolling process and resul­
ting in anisotropy in steel products'- 2 " 3 - 1 . Ductility of
manganese sulfide would meet t h e controlling de­
mand of inclusions for tire cord steel which requires
the deformation ability of inclusions. H o w e v e r ,
steel with too much sulfur and manganese sulfide
would lead to t h e formation of banded s t r u c t u r e in
steel plates and do h a r m to t h e quality of t h e final
products'- 4-8 - 1 . A lot of researches have been carried
out to study t h e behavior of sulfur in steel as well as
desulfurization methods'- 9-11 - 1 . It is well k n o w n t h a t
the converter has less desulfurization effect; as a r e ­
s u l t , desulfurization sometimes would mainly be
out-of-furnace refining process. High temperature, as
well as high-basicity, large-amount and low-oxidability
of refining slag, are of great benefit for desulfurization.
Theoretical research on desulfurization using high basic­
ity top slag has been done by many metallurgists as
well as t h e industrial application 1 - 12-153 . H o w e v e r ,
refining slags used in t h e production of tire cord
steel m u s t be of low basicity in order to control the
plasticity of non-metallic inclusions, which largely
limits t h e sulfide capacity of refining process^ 6 - 1 .
And there are few reports on theory and application
of desulfurization using low basicity top slag for tire
cord steel.
T h e r e f o r e , experiments were carried out to
study the desulfurization performance in the 72
grade tire cord steel refining process using low basic­
ity top slag based on t h e results of theoretical calcu­
lation, and t h e n industrial application tests were
performed to study the changes of sulfur content t o -

Foundation Item:Item Sponsored by National Key Basic Research and Development Program of China (2010CB30806); Central South University
Postdoctoral Funded Project of China (120961)
Biography:CHEN Shu-hao( 1983—), Male, Doctor, Lectureship; E-mail: chenshuhao021@163.com; Received Date: August 4, 2011
Issue 1 I n d u s t r i a l A p p l i c a t i o n of D e s u l f u r i z a t i o n U s i n g L o w Basicity R e f i n i n g S l a g in T i r e C o r d S t e e l · 27 ·

gether with plasticity of non-metallic inclusions in Table 1 Chemical composition in steel used in
s t e e l , so as to find a better composition range of re­ theoretical calculation
(mass percent, %)
fining slag for high quality tire cord steel product.
c Si Mn P S TO Al.
1 Theoretical Background 0.72 0.25 0.55 0.008 0.01 0.002 0.001
1.1 Basic principle N o t e : T O stands for total oxygen while Al, stands for
T h e basic principle of desulfurization in top slag acid-soluble aluminum.

refining can be described by the following equa­

tions 1[17-18] Table 2 Chemical composition of refining slag
2
[S] + ( 0 - ) = [ 0 ] + (S ~) 2
(1) used in theoretical calculation
fl ™Mgo/ «ΆΙ,Ο,/ _. . . Slag/
aCß\/RT . [Q] ' /a2" ♦ W(s2-) Factors
W[S]: (2) % % steel ratio
a<o 2 ~) · / s
2
Basicity 10 5 0.8-2.0 10 ' 100
_W(S) _ - A G?/RT . A W ' ) · /s
(3) MgO content 0 — 15 5 1.2 10 ' 100
W[S] <2[o] * / s 2 ~
5 ' 100-
w h e r e , [ z ] and (i~ ) stand for i in steel and slag r e ­ Slag/steel ratio 10 1.2
30 ■■ 100
spectively, while it>[;] is i content by mass·; / ; is ac­
tivity coefficient of i; at is activity of i; G is Gibbs
free energy of the reaction; and L s stands for sulfur the s l a g / s t e e l r a t i o , A 1 2 0 3 content in slag and M g O
partition ratio between slag and steel. The major factors content in slag were 1 to 1 0 , 5 % and 1 0 % respec­
affecting sulfur content in steel are the activity of tively. Changes of sulfur content in steel and sulfur
O 2 - and S 2 ~ in top slag as well as oxygen activity in partition ratio with basicity obtained by t h e r m o d y ­
liquid s t e e l , while the major factors affecting sulfur namic calculation are s h o w n in Fig. 1.
partition ratio between slag and steel are the activity
100 ■
of 0 2 ~ and the activity coefficient of S 2 ~ in top slag ^ " ^ V
300
H'|ij|
as well as oxygen activity in liquid steel. Oxygen ac­ 80
\ / '
tivity in liquid steel affects desulfurization perform­ Λ - 200
ance and it can change in a wide r a n g e , depending on
b 60 V / '
X /
many factors such as deoxidation, amount of F e O f 40
- 100
and M n O in refining s l a g , etc. T h e activity of O 2 - is
20
in refining slag is mainly determined by the activity
of basic oxides such as CaO and M g O in refining 0
0.f 1.2 1.6 2.0
s l a g , while the activity of S 2 ~ in refining slag is de­ R
termined by many factors. T o s u m , the main factors
Fig. 1 Influence of basicity on sulfur capacity at 1873 K
influencing desulfurization performance of refining
according to theoretical calculation
slag are basicity, M g O content and s l a g / s t e e l ratio.
Sulfur content in steel changes very little while
1. 2 Thermodynamic equilibrium calculation sulfur partition ratio keeps unchanged w h e n the ba­
T a k e 72 grade tire cord steel for e x a m p l e , and sicity of slag is less than 1. 2. However, sulfur content
use FactSage to calculate the desulfurization equilib­ in steel decreases rapidly while sulfur partition ratio
rium of s l a g / s t e e l reaction at 1 873 K with different increases rapidly with the increase of basicity w h e n
slag conditions, such as basicity, M g O content and the basicity of slag is above 1. 2. Sulfur content in
s l a g / s t e e l ratio. T h e basis of FactSage is minimum steel is less t h a n 0. 0 0 1 % and sulfur partition ratio is
Gibbs free energy principle and the " E q u i l i b " module more than 300 w h e n the basicity of slag reaches 2. 0.
of FactSage is used for this thermodynamic equilibri­ 1.2.2 MgO content
um calculation, accessing the compound and solution Sulfur capacity of top slag refining varying with
databases including FACT-SLAGA and FACT-FeLQ M g O content in the range of 0 to 1 5 % was calculat­
base-phase. Chemical compositions of experimental ed while the s l a g / s t e e l r a t i o , A 1 2 0 3 content in slag
steel are s h o w n in T a b l e 1 while slag in T a b l e 2. and basicity of slag were 1 to 1 0 , 5 % and 1.2 re­
1. 2. 1 Basicity spectively. Changes of sulfur content in steel and
Sulfur capacity of top slag refining varying with sulfur partition ratio with the M g O content obtained
basicity in the range of 0. 8 to 2. 0 was calculated while by thermodynamic calculation are s h o w n in Fig. 2.
 • 28 · Journal of Iron and Steel Research, International Vol. 20

factors, oxidability of refining slag also has a great

90 O-D-D. ■ D
- D
- ^ ■ influence on the desulfurization performance, which
can be described by the sum content of F e O and
/

4'
M n O in slag. Besides, the effect of kinetic condi­
80 ■

\ tions on desulfurization in refining is also very im­

p o r t a n t , which would limit the M g O content in the
70
is —
/
A ■
h
refining slag.

60 7^ Sulfur content control in tire cord steel is im­

1 1
0 5 10
WMgo/%
Fig. 2 Influence of MgO content on sulfur capacity at
1873 K according to theoretical calculation
Sulfur content in steel reduces gradually while
sulfur partition ratio increases gradually with the in­
crease of MgO content in slag under the thermodynamic
equilibrium state. This tendency is slight when MgO
content in slags is under 1 0 % , and then becomes rapid
with the increase of M g O content in refining slag.
1. 2. 3 Slag/steel ratio
Sulfur capacity of top slag refining varying w i t h
s l a g / s t e e l ratio in the range of 1 ! 100 to 60 ! 100
was calculated while the A 1 2 0 3 c o n t e n t , M g O con­
t e n t and basicity were 5 % , 1 0 % and 1. 2 respectively.
Changes of sulfur content in steel and sulfur parti­
tion ratio of s l a g / s t e e l reaction w i t h s l a g / s t e e l ratio
obtained by thermodynamic calculation are s h o w n in
Fig. 3.
Sulfur content in steel decreases rapidly with
the increase of s l a g / s t e e l ratio. T h o u g h s l a g / s t e e l
ratio has less effect on sulfur partition ratio between
slag and s t e e l , total sulfur in slag increases with the
increase of slag a m o u n t t h a t results in the decrease
of sulfur content in steel.
portant. H o w e v e r , plasticity control of non-metallic
inclusions is more significant for the final product
15
steel cord, which would largely limit the basicity,
M g O content as well as A 1 2 0 3 content of refining
slag. Therefore, in the next laboratory experiments,
basicity would be set for 0. 8, 1 . 0 , 1. 2 and 1. 4.
2 Laboratory Experiments
2.1 Sample preparation
T h e experiments were carried out in a silicon-
m o l y b d e n u m resistance furnace and the experimental
installations are shown in Fig. 4. T h e silicon-molyb­
denum heating rods arranged symmetrically in the
furnace body can provide a constant t e m p e r a t u r e
zone of less t h a n 2 000 K and t h e t e m p e r a t u r e devia­
tion between the actual t e m p e r a t u r e and the dis­
played t e m p e r a t u r e which is measured by platinum-
rhodium thermocouple is ± 2 K. Pre-melting s t e e l ,
with basic chemical composition s h o w n in T a b l e 1,
and prepared top slag were p u t - t o g e t h e r in a magne­
sium oxide crucible. T h e n , the crucible was set in the
constant t e m p e r a t u r e zone of the furnace. Slag was
the mixture of CaO, S i 0 2 , MgO and A 1 2 0 3 , all of
which are analytical pure grade. Both ends of the corun­
dum reaction tube were sealed with a fluorine rubber
ring respectively to ensure the pressure tightness of the
whole reaction system. A r g o n gas flow of 1. 50 L / m i n

Gas out

Slag
Crucible
Metal

Furnace tube

Si-Mo rods

0:100 10:100 20:100 30:100 Furnace body

Slag/steel ratio
Fig. 3 Influence of slag/ steel ratio on desulfurization
Thermocouple Argon in
performance at 1873 K according to theoretical calculation

1. 3 Other factors Fig. 4 Experimental apparatus used in laboratory

In addition to the above three thermodynamic desulfurization experiments with low basicity slag
Issue 1 Industrial Application of Desulfurization Using Low Basicity Refining Slag in Tire Cord Steel · 29 ·

was used during experimental process all the time from Table 4 Sulfur content in steel and top slag as well as
the bottom of the reaction t u b e to the top to provide a information of inclusions in experimental heats
non-oxidizing a t m o s p h e r e . T h e melts were held for Inclusions number/
Heat mm-2
60 min after the temperature reached 1 873 K. Finally tf[s] 1% >/% W[TO] /%
No.
the crucible containing melts was t a k e n out and MnS Oxide

quenched quickly in water. Steel and top slag in the 0.009 6 0.003 8 0.0018 19.47 9.26
0.009 2 0.007 8 0.0015 18.26 8.32
crucible were separated. T h e quality of steel used in
0.008 4 0.0160 0.0013 17.78 8.00
total 12 heats of laboratory experiments was kept
0.005 9 0.040 7 0.0010 16.63 7.14
basically unchanged and basic information of slags
0.009 7 0.002 9 0.0014 19.59 8.16
used in the experiments is s h o w n in T a b l e 3. 0.0091 0.0084 0.0013 18.37 8.20
0.006 3 0.0361 0.0012 17.09 7.83
Table 3 Basic chemical components of top 0. 009 1 0.0180 0.0013 18.29 8.06
slags used in laboratory experiments 0.007 7 0.015 3 0.0014 17.31 7.98
Heat wco/ w
siC-2 / wnigo/ W
AI2O3/ Slag/steel 10 0. 007 1 0.0143 0.0013 17.03 8.04
No. % % % % ratio 11 0. 006 5 0.013 3 0.0014 16.80 8.10
1 35.5 44.5 10 10 10 100 12 0. 006 1 0.0123 0.0012 16.59 7.95
2 40.0 40.0 10 10 10 100
3 43.5 36.5 10 10 10 100
4 46.5 33.5 10 10 10 100
5 49.0 41.0 0 10 10 100
6 46.5 38.5 5 10 10 100
7 41.0 34.0 15 10 10 100
8 43.5 36.5 10 10 5 :100
9 43.5 36.5 10 10 15 100
10 43.5 36.5 10 10 20 100
11 43.5 36.5 10 10 25 100
12 43.5 36.5 10 10 30 100

Fig. 5 Influence of basicity of top slags on sulfur

2. 2 Laboratory experimental results
capacity in laboratory experiments at 1873 K
Slag samples and steel samples were t h e n sent
to National Materials T e s t i n g Center of China. T h e n the same way sulfur partition ratio increases gradu­
total oxygen content and sulfur content in steel as ally from 0. 4 to 7 w i t h the increase of basicity of top
well as sulfur in slag were analyzed. In order to slag. T h e results are of good agreements with those
study the non-metallic inclusions in experimental of FactSage calculation.
steel, A s p e x , a new inspection tool which can per­
2. 3. 2 Effect of MgO content on sulfide capacity
form auto detection of inclusions and at the same
of slag
time record the information such as morphology, size
As shown in Fig. 6 sulfur content decreases linearly
and composition as well as number, was used.
with the increase of MgO content of top slag used in the
T h e chemical compositions of steels and slags as
well as the n u m b e r information of non-metallic in­
100 ■
clusions in steel after laboratory experiments are lis­
ted in T a b l e 4.

2. 3 Analysis of laboratory experiment results

2. 3. 1 Effect of basicity on sulfide capacity of slag
A s s h o w n in Fig. 5 , sulfur content in steel in la­
boratory experimental heats decreases significantly
with the increase of basicity of top slag used in the
experiments. Sulfur content is 0 . 0 0 9 6 % with the
basicity of 0 . 8 and 0 . 0 0 9 2 % with the basicity of WMg0/%

1 . 0 ; f u r t h e r m o r e , sulfur content is less t h a n Fig. 6 Influence of MgO content of top slag on sulfur
0. 0 0 6 % w h e n the basicity of refining slag is 1. 4. In capacity in laboratory experiments at 1873 K
 • 30 · Journal of Iron and Steel Research, International Vol. 20

experiments. Sulfur content is 0.009 7 % without MgO
and 0.006 3 % with the MgO content of 1 5 % . Sulfur
partition ratio increases gradually from 0. 3 to 6 w i t h
the increase of M g O content of top slag. T h e influ­
ence of M g O content on sulfur content and sulfur
partition ratio is some lower t h a n t h a t of basicity.
2. 3. 3 Effect of slag/steel ratio on steel content
in steel
Fig. 7 s h o w s t h a t sulfur content in steel decreases
markedly w i t h the increase of s l a g / s t e e l ratio in the
experimental heats. Sulfur content is 0. 009 1 % w i t h
the s l a g / s t e e l ratio of 5 to 100 and 0. 0 0 7 1 % with
t h a t of 20 to 100. F u r t h e r m o r e , sulfur content de­
creases to 0. 0 0 6 1 % w h e n the s l a g / s t e e l ratio is 30
to 100. Sulfur partition ratio keeps basically un­
changed while slag/steel· ratio increases from 5 ! 100
to 30 ! 100. T h e influence of s l a g / s t e e l ratio on sul­
fur content is o b v i o u s , while the actual situation is
that s l a g / s t e e l ratio m u s t be controlled below 10 to
100 during refining process in the steel production.
inclusion becomes large with the increase of sulfur
content in s t e e l , while the compositions of oxide in­
clusions change w i t h the increase of basicity as well
as M g O content of refining slags.
Basic parameters of top slag can be changed
flexibly in laboratory experiments so as to study sul·-
fide capacity of refining slag in a large varying
r a n g e , and results of laboratory e x p e r i m e n t s are of
good a g r e e m e n t s w i t h r e s u l t s of theoretical calcula­
tion by F a c t S a g e . H o w e v e r , basicity of refining
slag used in t h e production of tire cord steel m u s t
be a r o u n d 1. 0 to 1. 2 so as to achieve the plasticiza-
tion control of inclusions, which would not play a
better role in obtaining a better desulfurization effect
compared with high basicity refining slag. H o w to
reduce sulfur content in tire cord steel w i t h low ba­
sicity slag becomes a key question. Industrial trial
for 72 grade tire cord steel was carried out in one do­
mestic plant to study desulfurization as well as inclu­
sions control.

5 3 P l a n t Trial
100
^^W|S]
■
4 3.1 Production process and sampling plan
90 >V
3 150 t LD-RH-LF-Soft argon blowing-CC process
2 80 CO
was used in the production of 72 grade tire cord steel
and silicon-manganese alloy w a s added into the hot

■A
CO

r
70 1 steel to perform compound deoxidization while spe­
cial refining slag was added to make synthetic slag
60 0
I 1 washing. T w o special refining s l a g s , chemical com­
0:100 10:100 20:100 30:100 positions of which are s h o w n in T a b l e 5 , were added
Slag/steel ratio
in steel ladle during the vacuum t r e a t m e n t at R H ,
Fig. 7 Influence of slag/ steel ratio on desulfurization
L F refining process and tundish station in two series
performance in laboratory experiments at 1873 K
heats respectively.

2. 3. 4 Non-metallic inclusions in steel Sampling was performed at R H , L F , soft argon

A s s h o w n in Fig. 8 , the n u m b e r of sulfide inclu­ blowing and CC-tundish stations during plant trial.
sion increases w i t h the increase of sulfur content in Liquid steel w a s sampled by bucket sampler and slag
steel while t h a t of oxide inclusion keeps basically specimens were obtained using little iron dustpan.
unchanged. Further study indicates that size of sulfide Billets were also sampled. All the samples were
treated as it is treated in laboratory experiments.
20.0 oSulfide inclusions 9.5 =?
•Oxide inclusions 3?_ Table 5 Chemical compositions of refining
19.0 o.o I slag used in plant trial
18.5J
•
a Slag system R
WMgo/
%
TO
A1203/
%
TOFeo/
%
IfMno/
%
Ws/
%
·•
18.0
■§ ·• ·• a
β -: · H8.o
. -a -a
a •· 1.21 2.55 1.30 0.5 0. 45 0. 04
3 n
D o
17.0 o D 7.5 'S 1.02 1.13 1.18 0.7 0. 60 0. 05
0
■ 7.0 §
IfiO ■ ■ ' ■ Z
3 . 2 Test results and discussion
0.005 0.006 0.007 0.008 0.009 0.010
Sulfur contents 3. 2. 1 Sulfur content in steels and basic composi­
Fig. 8 Relationships between number of inclusions and tion of top slags
sulfur content in laboratory experimental steel Sulfur content in steels and the basic chemical
Issue 1 Industrial Application of Desulfurization Using Low Basicity Refining Slag in Tire Cord Steel · 31 ·

components of top slags during top slag refining
process were measured and results of t h e representa­
tive heats are presented in T a b l e 6.
3. 2. 2 Effect of top slag compositions on sulfur
capacity
It can be seen from the industrial test results
that sulfur content in steel increases at early refining
stage with rapidly decreased basicity of top slag be­
cause of the new added refining slags with basicity of
1. 21 or 1. 02. Basicity of top slags decreases slowly
during the refining p r o c e s s , from 1. 36 to 1. 15 and
1. 15 to 0. 95 respectively. H o w e v e r , sulfur content
in steel decreases gradually instead of increasing as a
result of combined effect of other factors such as MgO
content as well as oxidizing substances contained in top
slags during refining process. Relationships between
sulfur content in steel and basicity, M g O content as
well as the sum content of F e O and M n O of top
slags during refining process are shown in Fig. 9 ,
Fig. 10 and Fig. 11 respectively.

Table 6 Sulfur content in steel and basic components of slags during industrial production processes
Sampling R ™[S]/% VJlMgO)/'/' W(FeO+MnO)/%
station i ? = l . 21 «=1.02 £ = 1.21 K = l . 02 J ? = l . 21 K=1.02 J ? = l . 21 j R = l . 02
BOF end 4.18 3. 98 0.008 5 0.009 3 10.39 11.39 23.89 23.14
R H beginning 1.36 1. 15 0.009 6 0.0109 6. 16 5.45 4.66 6.08
R H end 1.26 1. 13 0.009 2 0.0101 6. 17 5.40 4.18 5.63
L F first stage 1.24 1.07 0.008 4 0.0091 7. 13 6.61 3.67 5.27
L F second stage 1.25 1.08 0.007 2 0.008 6 6.97 6.50 3.54 4.81
L F end 1.24 1.04 0.006 4 0.007 9 7.37 9.72 2.50 4.76
Ar beginning 1.22 1.02 0.006 7 0.008 2 8.30 7.97 1.51 2.93
Ar end 1.20 0.98 0.006 3 0.007 5 9. 13 8.64 1.29 2.68
Tundish 1.15 0. 95 0.008 5 0.009 3 5.96 5.28 7.22 8.02

110
magnesia ladle is eroded gradually and M g O content
of slag increases gradually in the refining process. T h e
Second heat Α*=1.0
100

90

70

LD RH1 RH2 LF1 LF2 LF3 Arl Ar2 Tundish

Station
RH1 - RH beginnings RH2—RH end; LF1—LF first stage;
LF2—LF second stage; LF3—LF end; Fig. 10 Influence of MgO content of top slags on
Arl—Ar beginning; Ar2—Ar end. sulfur content in steel during plant trial process
Fig. 9 Influence of basicity of top slags on sulfur
content in steel during plant trial process 110 o

T h e r e is an obvious tendency during the produc­ 100 • o y

o
tion process t h a t sulfur content in steel with initial
. o .
refining slag basicity of 1. 21 is lower t h a n that with b 90

basicity of 1. 02. It is also found t h a t sulfur content

X o /
M o 0
* 80 / 0
decreases with the increase of M g O content in slag
while increases with the increase of the s u m content 70
o o
of F e O and M n O . M g O content is high at B O F end o
0
resulting in low sulfur content in steel. H o w e v e r , fiO 0 / 1 1 ' I ' 1
1 4 5 6
M g O content of slags decreases greatly at the R H >f(FeO+MnO:/%

and tundish stations because the new added refining Fig. 11 Influence of sum content of FeO and MnO of
slags are of low basicity and low M g O content. T h e top slags on sulfur content in steel during plant trial process
 • 32 · Journal of Iron and Steel Research, International Vol. 20

s u m content of F e O and M n O is quite high at the LD
end because of the high oxidizability B O F slag and
decreases gradually because of the new added refi­
ning slag of low oxidizability. Sulfur content in steel
decreases along w i t h the refining process and increa­
ses at t u n d i s h suddenly because of the a b r u p t in­
crease of the s u m content of F e O and M n O which is
mainly caused by secondary oxidation.
3. 2. 3 Composition and plasticity of non-metallic
inclusions
T h e benificial factors for desulfurization are
high basicity, high M g O content and low oxidability
of refining slag. However, composition demand for re­
fining slag on the plasticity control of inclusions is oppo­
site in some extent. Plasticity control for inclusions,
mainly for oxide inclusions, in the t w o heats with
different initial refining slags is not the same. Com­
position distribution of oxide compound inclusions in
t h e billets projected in M n O - S i 0 2 - A l 2 0 3 system dia­
g r a m is s h o w n in Fig. 12. It can be seen from Fig. 12
t h a t plasticity of oxide inclusions is well controlled in
both t w o heats. T h e ratio of composition of oxide
inclusions located in the low-melting-point area, of
which melting t e m p e r a t u r e is below 1573 K in the
zone surrounded by the bold line shown in Fig. 12, is
more than 9 0 % in low basicity heat while 8 0 % in the

1.00 0 1.00
0.75 1.00 0 0.25 0.50 0.75 1.00
MnO A1203 MnO A1203
Mass fraction

Fig. 12 Composition distribution of oxide compound inclusions in billets projected in MnO-Si02-Al203

system diagram with basicity of 1. 02 (a) and 1. 21 (b)

heat of initial basicity of 1. 2 1 . T h e plasticity of ox­
ide compound inclusions is a little better controlled
in the low basicity heat.
Technological parameter such as s l a g / s t e e l ratio
can hardly be changed optionally during industrial
test process because of t h e specificity of industrial
production t h a t could limit the application of t h e o ­
retical calculation and laboratory experimental r e ­
sults. H o w e v e r , t h e industrial test has achieved a
very good effect in b o t h control of sulfur content and
inclusions in general. Basicity is controlled in the
range of 1. 0 to 1. 2 and M g O content in the range of
5 % to 10. 5 % as well as sum content of F e O and
M n O in the range of 1 % to 8 % during refining
p r o c e s s , and t h e n sulfur content in billet is in the
range of 0 . 0 0 7 % to 0 . 0 0 8 1 % . A s s l a g / s t e e l ratio
can hardly be adjusted too high during refining
p r o c e s s , B O F roughing slag amount should be con­
trolled as little as possible, t h u s more refining slag
can be added into ladle during the subsequent refi-
ning p r o c e s s , enhancing the refining s l a g / s t e e l ratio
and reducing the sum content of F e O and M n O of fi­
nal slag. Finally, better performance in desulfuriza­
tion as well as inclusions control by top slag refining
in industrial production can be obtained.
4 Conclusions
1) Desulfurization effect of refining with low
basicity top slag was studied t h r o u g h t h e r m o d y n a m -
ic calculation using FactSage. Sulfur content in steel
decreases while sulfur partition ratio increases grad­
ually along with the increase of basicity and M g O
content of refining slag.
2) Laboratory study for the sulfur capacity of
low basicity slag was carried out t h r o u g h changing
basicity of slag (0. 8 — 1. 4 ) , MgO content of slag (0 —
1 5 % ) and s l a g / s t e e l ratio (5 · 100 — 30 ! 1 0 0 ) , and
the results are of great agreements with those of
theoretical calculation.
3) Study for production test process of 72 grade
Issue 1 I n d u s t r i a l A p p l i c a t i o n of D e s u l f u r i z a t i o n U s i n g L o w Basicity R e f i n i n g S l a g in T i r e C o r d S t e e l
tire cord steel was carried out in a domestic plant
and it is found that sulfur content in steel decreases
gradually during refining process. The plasticity of
inclusions is well controlled in both the two heats
while a little better in low basicity heat.
4) Strictly controlling BOF roughing slag amount
and then adding more low basicity (1. 0 — 1. 2) refining
slag during the subsequent refining process can off­
set the disadvantages of that the slag/steel ratio can
hardly be too high in industrial production, and then
both sulfur content and inclusions in steel can be
well controlled.
References:
[l] W A N G Xin-hua. Economical Cleanliness and Rational Produc­
tion Technology for Common Hot Rolled Steel Products [ J ] ,
Henan Metallurgy, 2003, 11(6) : 3 (in Chinese).
[2] Taisei Nakayama, Noriyuki Honjou, Takashi Minaga, et al.
Effects of Manganese and Sulfur Contents and Slab Reheating
Temperature on the Magnetic Properties of Non-Oriented
Semi-Processed Electrical Steel Sheet [ J ] . Journal of Magnet­
ism and Magnetic Materials, 2 0 0 1 , 2 3 4 ( 1 ) : 55.
[3] Wakoh Masamitsu, Sawai T a k a s h i , Mizoguchi Shozo.
of S Content on the MnS Precipitation in Steel With Oxide Nu­
clei [ J ] . ISIJ International, 1996, 3 6 ( 8 ) : 1014.
[4] Lv B , Zhang F C, Li M , et al. Effects of Phosphorus and Sul­
fur on the Thermoplasticity of High Manganese Austenitic Steel
[ J ] . Materials Science and Engineering, 2010, 5 2 7 A ( 2 1 / 2 2 ) :
5648.
[5] Jeon Soon-Hyeok, Kim Soon-Tae, Lee In-Sung, et al. Effects
of Sulfur Addition on Pitting Corrosion and Machinability Be­
havior of Super Duplex Stainless Steel Containing Rare Earth
Metals: Part 2 [ J ] . Corrosion Science, 2010, 5 2 ( 1 0 ) : 3537.
[6] Domizzi G , Anteri G , Ovejero-Garcia J. Influence of Sulphur
Content and Inclusion Distribution on the Hydrogen Induced
Blister Cracking in Pressure Vessel and Pipeline Steels [ J ] ,
Corrosion Science, 2 0 0 1 , 4 3 ( 2 ) : 325.
· 33 ·
[7] Siyasiya C W , Stumpf W E. T h e Influence of Sulphur Content
on the Static Recrystallisation of Cold Worked Low Carbon
Aluminium-Killed Strip Steels [ J ] . Materials Science and Eng­
ineering, 2008, 4 9 4 A ( l / 2 ) : 188.
[8] Abd El Meguid E A , Mahmoud N A , Abd El Rehim S S. T h e
Effect of Some Sulphur Compounds on the Pitting Corrosion of
Type 304 Stainless Steel [ J ] . Materials Chemistry and Physics,
2000, 6 3 ( 1 ) : 67.
[9] Jagdish C, Agarwal, John A , et al. Economic Benefits of Hot
Metal Desulfurization to the Iron and Steelmaking Processes
[ C ] // Ironmaking Conference Proceedings. Pennsylvania:
[ s . n. ] , 1 9 8 1 : 146.
[10] Nzotta M M , Du Si-chen, Seetharaman S. Sulphide Capacities
in Some Multi Component Slag Systems [ J ] . ISIJ Internation­
a l , 1998, 3 8 ( 1 1 ) : 1170.
[11] Nzotta M M , Du Si-chen, Seetharaman S. A Study of the Sul­
phide Capacities of Iron-Oxide Containing Slags [ J ] . Metallur­
gical and Materials Transactions, 1999, 3 0 B ( 1 0 ) : 909.
[12] Derin Bora, Suzuki Masanori, Tanaka Toshihiro. Sulphide
Capacity Prediction of Molten Slags by Using a Neural Net­
work Approach [ J ] . ISU International, 2010, 5 0 ( 8 ) : 1059.
[13] Yoshinori Taniguchi, Nobuo Sano, Seshadri Seetharaman.
Sulphide Capacities of C a O - A l 2 0 3 - S i 0 2 - M g O - M n O Slags in
the Temperature Range 1 673 —1 773 K [ J ] , ISIJ Internation­
al, 2009, 4 9 ( 2 ) : 156.
[14] Gibert S, Monos G G , Turkdogan E T. Ladle Refining of
Effects Steel Using an Exothermic Synthetic Slag [ C ] / / S t e e l m a k i n g
Conference Proceedings. T o r o n t o : [ s . n. ] , 1988: 291.
[15] Tanaka Toshihiro, Ogiso Yumi, Ueda Mitsuru, et al. Trial
on the Application of Capillary Phenomenon of Solid CaO to
Desulfurization of Liquid Fe [ J ] , ISIJ International, 2010, 50
( 8 ) : 1071.
[16] W A N G Li-feng, Z H U O Xiao-jun, Z H A N G Jiong-ming, et al.
Controlling Inclusion Composition in Steelmaking Process for
T y r e Cord Steel [ J ] . Journal of University of Science and
Technology Beijing, 2003, 25(4) : 308 (in Chinese).
[17] Richardson F D. Physical Chemistry of Melts in Steelmaking
[ D ] . New York; Academic P r e s s , 1974.
[18] Görnerup M. Studies of Slag Metallurgy in Stainless Steel­
making [ D ] , Stockholm: Department of Metallurgy, Royal
Institute of Technology, T R I T A - T P M , 1997.