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JOURNAL OF IRON AND STEEL RESEARCH, INTERNATIONAL. 2012, 19(4): 22-27

Effect of Boron on Morphology of Inclusions in Tire Cord Steel

CUI Huai-zhou'?' , CHEN Wei-qing'
(1. State Key Laboratory of Advanced Metallurgy, School of Metallurgical and Ecological Engineering, University of
Science and Technology Beijing , Beijing 100083, China; 2. Metallurgical Process Research Institute, Central
Iron and Steel Research Institute, Beijing 100083, China)

Abstract: &03 was added to tire cord steel during refining in a carbon tube furnace. T h e influence of boron on the
deformability of oxide inclusions was studied by metallographic and scanning electron microscope ( SEM) observa-
tions. The melting points of boron-bearing compound oxide inclusions were calculated using Factsage software. T h e
results showed that the main inclusion was a boron-bearing compound oxide and the deformation properties of the in-
clusions were clearly improved by adding B, 0 3 . As the boron content was increased from 0. 004 6 % to 0. 039 % , the
proportion of long strip type inclusions changed slightly and the number of inclusions decreased. T h e low-melting
point areas of the MnGSiOz-A12O3 and CaGSiOz-AIZO3 ternary system increased with the addition of & 03.Moreo-
ver, the area increased with the increase of &03 content. Clear improvements in the deformation ability of the inclu-
sions occurred when the & O3 mass percent rose to 5 % in the CaGSiO, -AlzO3 inclusion system and to 10 % in the
MnGSiOz-Alz0 3 inclusion system.
Key words: boron; tire cord steel; inclusions morphology

The main function of boron is t o improve the
hardenability of steel"]. T h e hardenability of hard-
ened and tempered steel can be dramatically en-
hanced by adding less than 0.003% by mass boron
to steel. Boron can not only lower the strength of
low-carbon soft wire steel and the strain ageing' in
the cold-working wiredrawing , but also
lower the strength of hot rolled sheets produced by
the compact strip production ( CSP ) p r o ~ e s s [ ~ ,- ~ ]
which also improves further cold rolled processes.
Tire cord steel is usually drawn into dimension of about
+O. 15 mm - 0.38 mm. T h e inclusion is one of the
key factors for wirebreaking in wire drawing process.
It is important and necessary to control not only the
quantity and sizes of inclusions, but also their de-
formation performance. T h e deformation perform-
ance of inclusions is usually controlled by adjusting
the composition of the refining slag, whose basicity
is about 1. Oc6-71. T h e results in referenceCe1show
that the deformation performance of inclusions can
be significantly improved by adding boron to low-
carbon steel. T h e research results of K A Ridal and
J D H HughesLg1show that the presence of B2O3was
identified by a neutron autoradiographic technique in
MnO-Al' 0,-SiO, inclusions of stainless steel with
boron, which markedly decreased the melting point
of silicate inclusions and increased their ductility in
the hot rolling process. T h e effect of boron on inclu-
sions morphology in tire cord steel has not been
studied until now. The function of boron for inclusion
deformation performance was investigated in this work
by adding boron to tire cord steel, in order t o provide a
new idea for inclusion ductility.
1 Experimental Procedure
The experimental materials of 72A tire cord steel
wires were obtained from a domestic steel enterprise,
and the chemical composition is shown in Table 1. The
amount of slag is 10% of the mass of the wire and the
composition of the slag is shown in Table 2.

Table 1 Chemical composition of raw material (mass percent, % )

~ ~~~ ~~

C Si Mn P S Cr Ni cu Ca A1
0.72 0.26 0.53 0.008 0.012 0.024 0.008 0.006 <0.0005 0.002

Biography:CUI Huaikzhou(l980-), Male, Doctor; E-mail: xlfdcu@sohu. corn; Received Date: February 23, 2011
Issue 4 Effect of Boron on Morphology of Inclusions in Tire Cord Steel 23 a

Table 2 Composition of slag (mass percent, %) steel 3 min later. After 1 h of constant heating in the
CaO SiOz A1203 MgO furnace, the molten steel was cooled to room tem-
46. 5 46. 5 2 5 perature.
2 ) T h e steel ingots were kept at 1000 "Cfor 1 h
in a heating furnace. An air forging hammer was
Three batches of tire cord steel containing boron used t o forge them into wires +7 mm. Afterwards,
and one batch without boron were smelted in a car- the wires were incised along the central axis in order
bon tube furnace. T h e chemical compositions of the to prepare metallographic specimens.
samples are shown in Table 3. T h e specific steps of 3) These specimens were observed in a 640 times
the experiment are as follows. metallographic microscope. Each specimen was ob-
1) T h e steels were smelted in a magnesia cruci- served in 100 fields of view and the inclusions'
ble in a carbon tube furnace protected by argon at a shape, quantity and sizes were statistical measured.
temperature of 1600 'C.A mixture of the slag was Typical inclusions in the specimens were analyzed by
added after the wires had melted. Then B 2 0 3 , which energy spectrum analysis in an SEM to identify their
was packed in iron sheet, was inserted into the liquid ingredients.

Table 3 Chemical composition of tested steels and B recovery ratios (mass percent, %)
No. C Si Mn P S A1 B B recovery ratios
1 0. 69 0. 17 0.47 0.007 0.007 <0.002 - -
2 0. 67 0. 18 0. 44 0.008 0.005 <O. 002 0.004 6 8. 3
3 0. 66 0. 18 0. 51 0.006 0.010 (0.002 0.007 6 11. 7
4 0. 76 0. 20 0. 45 0.010 0.009 <0.002 0.0180 21.4
5 0. 77 0. 1 2 0. 4 1 0.009 0.006 (0.002 0.039 0 37. 9

2 Results and Discussion comparison, inclusions in boron-bearing tire cord

steel showed an observable improvement on the de-
2 . 1 Effect of boron on deformation performance of formation performance. Most of these were in the
inclusions in tire cord steel shape of strips along the forging direction, as shown
Observation of specimens in the metallographic
in Fig. 2. Table 4 shows the composition of typical
microscope indicated that the main inclusions in all inclusions.
the specimens could be categorized into two types:
Fig. 3 shows that the proportion of deformable in-
one was a rod-like deformable inclusion, and the
clusions (length-width ratio >3) in boron-bearing steel
other was irregular and not deformable. Since rod-
is visibly higher than that in steel without boron. This
like inclusions contain both oxide inclusions and
manganese sulphide inclusions, only the rod-like ox-
ide inclusions are considered here.
T h e morphologies of inclusions in steels were
different in those with and without boron. Inclusions
in tire cord steel without boron were generally not
deformable; typical examples are shown in Fig. 1. By

Fig. 1 Morphology of inclusions in steel without boron Fig. 2 Morphology of inclusions in steel containing boron
 24 * Journal of Iron and Steel Research, International VOl. 19

Table 4 Composition of typical inclusions obtained by SEM

Length-width
Samples Fig. Composition of inclusions (mass percent) / %
ratio
The steel without boron Fig. 1 ( a ) 2 CaO 30. 13, MgO 17.87, Si0z 45. 55, Alp03 6.45
Fig. 1 ( b ) 1. 7 MnO 13.62, MgO 5.97, SiOz 74. 11, A1203 6.29
The steel with boron Fig. 2 ( a ) 19 MnO 9. 6 , MgO 0. 79, siop 53. 96, Alz03 0. 93, *BZO3 34. 7
Fig. 2 ( b ) 31 CaO 34.1, MnO 0.95, MgO 19.41, SiOp 10. 37, A1203 12.82, * BpO3 22.34
Fig. 2 (c) 5 CaO 47.36, MnO 7.63, MgO 6.24, SiOp 26.74, Alp03 12.04
Fig. 2 (d) 6 MnO 13.62, MgO 5. 97, SiOz 74. 1 1 , Alp03 6.29
Fig. 5 2. 5 B 31.29, N 62.97, A1 0.27, Mn 5.47
Note: As one of the light elements, the boron content determined by spectral analysis was not exact, therefore, the results are for
reference only.

ber of inclusions is just about equal to the value for

steel without boron. When the boron mass percent is
increased to 0.007 6 % or more, the number of inclu-
sions decreased.
The energy spectrum analysis from the SEM
testified that oxide inclusions in steel not containing
boron mainly existed as CaOSi0,-Al,03, MnOSi0,-
Al, O3 and Ca0-MnO-SiO2-AlZ0,. T h e majority of
inclusions had some MgO, which probably arose
from the material of the magnesia crucible.
wn/%
Compound oxide inclusions in boron-bearing
Fig. 3 Effect of w B on proportion of steel in the form of long strips, of width smaller
deformed long strip inclusions than 2 pm , had satisfying deformation performance.
T h e energy spectrum analysis proved that the inclu-
ratio is 31% in steel without boron, but more than 80%
sions containing boron were B, 03-Mn0-Si02-A1,0 3 ,
in boron-bearing steel. As the boron mass percent
B, 03-CaO-Si0,-A12 0, compound inclusions, which
varied from 0.004 6 % to 0. 039%, the proportion of
are shown in Table 4. T h e deformation performance
deformable inclusions changed a little. Table 5 shows
of long strip inclusions in Fig. 2 (c) and Fig. 2 (d) is
the number of inclusions in each specimen which was worse than Fig. 2 ( a ) and Fig. 2 ( b ) , but much bet-
observed in 100 fields of view. Fig. 4 indicates that
ter than ones in steel specimens without boron. In
when the mass percent of boron is 0.004 6 % , the num-
the range of sensitivity of the energy spectrum anal-
ysis, boron is not detected in Fig. 2 ( c ) and Fig. 2
Table 5 Number of inclusions in 100 fields of view
( d ) , probably because the boron content is low, so
Item Data
that the deformation performance of inclusions c and
Boron content of d is worse than that of a and b in Fig. 2.
0 0.0046 0.0076 0.018 0.039
specimens/%
In addition, there are a few non-deformable
Number of
inclusions/piece
37 39 25 18 15 bindings of B-N in the boron-bearing steel, which
are mainly of a knobbly shape, as shown in Fig. 5.
T h e composition of this sample reveals that when
the mass fraction of [B] (mass percent) in steel is
B
.-
zx- 6 0.0046%, the [N] (mass percent) is 60X10-6 and
c 'E the [0] (mass percent) is 3 6 X 1 0 - 6 . T h e result cal-
5 E
culated by Eqn. ( 1 ) shows that the precipitation
temperature of BN in austenite is 1153 "C.In order
z to decrease the number of BN, it is necessary to re-
0 duce the content of nitrogen in the steel.
0 0.004 6 0.0076 0.018 0.039
M lgKBN=Ig(W[B] w[N] >=--l 3970+5. 24 (1)
T
Fig. 4 Effect of w B on number of inclusions
Issue 4 Effect of Boron on Morphology of Inclusions in Tire Cord Steel * 25
~

2 . 2 Effect of boron on inclusions' melting points in

tire cord steel
T h e deformation performance of inclusions in
steels mainly depends on the melting points of the
inclusions. Inclusions, when the melting points are
below 1 4 0 0 'C , exhibit good deformation ability in
the rolling process. T h e ingredients of the compound
inclusions Mn0-Si02-A1, 0 3 and CaO-SiO, -A&0 3 in
tire cord steel are usually controlled in the shaded ar-
eas of Fig. 6"01.
T h e melting points of compound inclusions such
as B, 0,-CaOSi0,-Al, 0, and B, O,-MnOSiO,-Al, 0,
in tire cord steel were calculated using Factsage soft-
Fig. 5 Binding of BN ware. Fig. 7 shows the quaternary system phase dia-
SiOz

MnO Mass percent& A1203 CaO Mass percent&

Fig. 6 Plastic area of inclusions for MnO-SiOz-Alr03 system (a) and CaO-Si02-AIz03system (b)

.. ._

Ca00.9 O.i 0.5 0.3 0.lAI,cL,Cao0.9 0.7 0.5 0.3 O.lA.QTCa00.9 O . i 0.5 0.3 0.1 M.D, Ca00.9 0.7 0.6 0.3 0.1 N L b

&lass fracuons/(Si@+CaO+A201) M a s frarartrons/(Si&+CaO+A&) Mass fracuons/(Si&+CaO+A20,)

(a) wtl,o,=O; (b) w%03=1%; ( c ) ws,o,=2%; (d) W B , O , = ~ % ;

( f ) ~ B , o , =15% i
( e ) w%03= l o % ; (g) wgZo3=35%.

Fig. 7 Plastic area (G1400 "c ) of inclusions of different wsZo3 for Bz03-CaO-SiOz-Al~O~ system
 * 26 - Journal of Iron and Steel Research, International Vol. 1 9

gram of I$ 03-CaO-SiOz-Alz0 3 with 0 , 1% , 2 % , 5 % , that inclusions from the ternary system CaO-SiO, -
10% and 15% & 0 3 (mass percent), respectively. Al, 0, transform the quaternary system Bz03-CaO-
T h e summary in Fig. 8 indicates that the proportion Si0,-Al,03 inclusions, and the area of low melting
of the areas of the ternary phase diagrams with low point (<1 4 0 0 C) is enlarged with the increase of
melting point oxides ((1 400 'C)increases with in- B,03 in the inclusions. T h e area changes a little
creasing & 0 3 in the inclusions. These two graphs show when the B,03 content is below 5 % , but when it ex-
ceeds this critical point, the area becomes signifi-
g"' cantly larger, and the effect is dramatic.
g60 Fig. 9 shows the quaternary system phase dia-
8 grams of B2O,-MnO-SiOz-Alz 0 3 with 0 , l % , 2 % ,
40
d 5 %, 10% and 15% B , 0 3 (mass percent). Again,
2 20
'G
Fig. 10 indicates that the proportion of the areas of
3 the ternary phase diagrams with low melting points
c o ((1 400 "C) increases with the increase of B,03 in
0 1 2 5 1 0 1 5 3 5
"~O'P
the inclusions. It is apparent that the low melting
Fig. 8 Plastic area proportion of inclusions with different point area in the diagram increases after adding
wszo3 for B, 03-CaO-Si0,-AI, O3 Bz0,. When the B, O3 content in inclusions is equal to

MnO0.Y 0.7 0.5 0.3 0.1 AI&

Mass fraction Mass Mons'@iG+MnO+AILM

of the B, 03-CaO-Si0,-Alz 0 3 and B, 0,-MnO-SiOz-

le f i n 1 I
Al, 0, compound inclusions can be dramatically ex-
tended. T h e results of experiments in the laboratory
also proved that the fraction of deformable inclu-
sions apparently increased because B, O3 has lowered
the inclusion melting point. In addition, the number
of inclusions declined as the boron content in the
0 1 2 5 10 15 35 steel increased, probably because the increase causes
"BL(I,fi the melting points of partial inclusions to be re-
Fig. 10 Plastic area proportion of inclusions with different duced, so that the inclusions are removed in the liq-
wB, o3 for BZ0,-MnO-SiO, -A&0, uid phase.
G Bernardc"' has shown that when the content
10% or above, a significant effect can be seen. of boron in steel exceeds 0. 0 0 7 % , a low melting
From all these observations, when the B z 0 3 point Fe-C-B eutectic will appear on the grain
content is more than 5 % and l o % , the plastic areas boundaries. This can cause hot brittleness and de-
Issue 4 Effect of Boron on Morphology of Inclusions in Tire Cord Steel
grade hot workability, so the amount of boron in
steel should be carefully chosen. According to these
results, there is a significant effect on the ductility
of inclusions when the mass percent of boron in steel
is about 0. 004 6 % , so it is appropriate to control the
B mass percent in steel to be less than 0. 005%. Also,
reference"" reports that boron has little effect on
the harden-ability of high carbon steels. It is neces-
sary to further study the effect on harden-ability if
B z 0 3is t o be added to tire cord steel.
3 Conclusions
1) T h e deformation performance of compound
oxide inclusions in steel can be markedly improved
by adding B 2 0 3 to tire cord steel. The ductility of
inclusions in steel can be apparently improved when
the B mass percent in steel is 0. 004 6%. The proportion
of deformable inclusions in boron-bearing steel was visi-
bly higher than that in the steel without boron.
2) Compound oxide inclusions in boron-bearing
steel are mainly in long strip form, the width of
which are smaller than 2 p m , and have satisfactory
deformation performance. The inclusions containing
boron were €$ O3-MnCFSiOz-Alz0, , €$ 0,-CaCFSiOz-
Alz03compound inclusions, with a few BN.
3) T h e results of the Factsage calculation indi-
cate that when the B z 0 3 mass percent is more than
5 % and 10 % , plastic areas of B, O3-Ca0-SiO2-AlZ 0 3
and B, 03-MnO-SiOz-A120 3 compound inclusions can
be dramatically extended. The plastic area increases
as the B z 0 3content in the inclusions increases.
4) In order to improve the deformation per-
formance of compound inclusions in tire cord steel
and avoid degradation of hotworking performance, it
* 27 *
is important to restrict the boron content in steel to
less than 0. 005%.
References :
Central Iron and Steel Research Institute. Boron Steel Research
Works Collection [MI. Beijing: Metallurgical Press, 1981 (in
Chinese).
LI Wen-ying, CHEN Wei-qing, YUAN Hui. Investigation on
Strain Aging of Boron Containing Low Carbon Steel Wire Rod
[J]. Iron and Steel, 2006, 41(5), 78 (in Chinese).
YUAN Hui, LI Yong-dong, CH EN Wei-qing. Developmental
History and Present Situation of Low-Carbon Steel With Boron
[J]. Shougang Keji, 2005(6), 21 (in Chinese).
XIAO Li-jun, QIU Sheng-tao, LIU Jia-qi, et al. Softening
Mechanism of Low-Carbon Al-Killed Steel Strip Produced by
TSCR Route [J]. Iron and Steel, 2006, 41 ( 4 ) : 66 (in Chi-
nese).
FAN Ding-dong, ZHANG Jian-ping, XIAO Li-jun. Effect of
Boron Micro-Alloying on Microstructure Precipitates and Yield
Strength of SPHC Steel [J]. Iron and Steel, 2006, 41(9): 60
(in Chinese).
Fujimoto H , Soejima T, Matsumoto H. Development of ladle
Arc Refining Process [J]. Iron and steel, 1988, 74(10) : 74
(in Chinese).
Mimure T, Ogawa K , Maeda S. Shape Control of Inclusions in
Wire Rods for Steel Tire Cord [J]. R and D Kobe Steel Techni-
cal Report, 1989, 39(4): 77.
YE Fei, CH EN Wei-qing, ZHOU Xin-long. Effect of Boron on
Inclusion Morphology in Low Carbon Steel [J]. Iron and Steel,
2007, 42(10): 76 (in Chinese).
Ridal K A , Hughes J D H. Occurrence of Boron in Oxide Inclu-
sions in Steel [J]. Journal of the Iron and Steel Institute,
1967, 205(2): 183.
Bernard G, Ribound P V , Urbain G. Oxide Inclusions Plastic-
ity [J]. La Revue de MetallurgieCTT, 1981, 78(5) : 421.
Louis Rohl. The Manufacture and Use of Boron Steels in the
U. S. A [J]. Journal of the Iron and Steel Institute, 1954,
176: 173.
ZU Rong-xiang. Influence of Carbon and Alloying Elements
on the Properties of Spring Steel [J]. Journal of the Iron and
Steel Institute, 1986, 6 ( 4 ) , 59 (in Chinese).