Author’s Accepted Manuscript

Effect of B4C on the properties and microstructure

of Al2O3 -SiC-C based trough castable refractories

Jun Wu, Naijing Bu, Hongbo Li, Qiang Zhen

www.elsevier.com/locate/ceri

PII: S0272-8842(16)31866-1
DOI: http://dx.doi.org/10.1016/j.ceramint.2016.10.101
Reference: CERI13980
To appear in: Ceramics International
Received date: 9 June 2016
Revised date: 16 October 2016
Accepted date: 16 October 2016
Cite this article as: Jun Wu, Naijing Bu, Hongbo Li and Qiang Zhen, Effect of
B4C on the properties and microstructure of Al 2O3 -SiC-C based trough castable
r e f r a c t o r i e s , Ceramics International,
http://dx.doi.org/10.1016/j.ceramint.2016.10.101
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 Effect of B4C on the properties and microstructure of Al2O3
-SiC-C based trough castable refractories
Jun Wu a, Naijing Bu a*, Hongbo Li b, Qiang Zhen a*

a Research Center of Nano Science and Technology, Shanghai University, Shanghai,

200444, China
b Shanghai Lier Refractories Co. Ltd., Shanghai, 200949, China

Abstract: The effect of B4C addition (0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%) on
properties and microstructure of Al2O3-SiC-C (ASC) based trough castables was
studied in this paper. The results showed that the bulk density of samples after firing
at 1450 °C decreased when the addition of B4C was over 1 wt%. The cold modulus of
rupture of samples improved significantly with the addition of B4C when the treating
temperature was over 1100 °C. Among them, sample with 1.5 wt% of B4C had the
best anti-slag performance and thermal shock resistance. The SiC fibers were formed
in the non-oxidized zone of ASC castables with addition of B4C after firing at
1450 °C in air condition. The obtained fibers rooted in the walls of inner micropores
of samples with the diameter of 50-200 nm, and the lengths of 10-50 µm. The
experiment revealed the nucleation of SiC started at about 1000 °C, and then the
growth of SiC fibers happened at higher temperature in a favorable condition. A
stepped twin structure perpendicular to the growth direction of fibers could be
observed. Finally, the growth mechanism was interpreted by thermodynamic
calculations.

Keywords：In-situ formation; SiC fibers; Al2O3-SiC-C castable refractories; B4C;

thermodynamic calculations.

1. Introduction
Castable refractories based on Al2O3-SiC-C have been widely used as the major
blast furnace troughs owing to their excellent anti-slag performance and good
resistance against thermal shock at elevated temperature [1-4]. However, with the
development of smelting technology, better properties of ASC castable refractories are
required to meet the demands. At present, the improvement of service life of ASC
castable refractories mainly base on three methods: the promotion of slag resistance
[5,6], anti-oxidation performance [7] and mechanical properties [8]. Furthermore, In
situ formation of one-dimensional structure has also caught the attention of many
researchers. For instance, many carbon fibers were formed in the ASC castable

*
Corresponding authors. Tel: +86 21 66137276.
E-mail address: bunaijing@163.com (Naijing Bu), qzhen@staff.shu.edu.cn (Qiang Zhen).
composites by using the catalyst of nano Ni in the matrix [9]. Al2O3-C refractories
could obtain higher cold modulus of rupture due to the formation of SiC fibers and
multi-walled carbon nanotubes [10].
Carbon and SiC have the merits of high thermal conductivity and nonwettability
by liquid slag. However, the main drawback of SiC and carbon is their high
susceptibility to oxidation at high temperature [11-14]. Haibin Zuo et al. studied the
oxidation behavior and kinetics of Al2O3-SiC-SiO2-C composite in different
atmospheres [15-16], and they found that the material at 1200 °C had better resistance
to oxidation because of the formation of protective layer in air. In order to improve the
resistance to oxidation, the antioxidants have often been applied, such as metallic Al
and Si, Al4SiC4, B4C [7,17,18]. Recently, Liu et al. [19] reported that the addition of
microsilicon could greatly improve the anti-oxidation performance of
Al2O3-SiC-SiO2-C castable. One of advantages for the application of B4C in
carbon-containing refractories is its ability of preferential oxidation, thus improving
the service life of refractories [20-22]. In addition, the formed low melting phase can
further increase the anti-oxidation performance by forming a protective layer on the
surface of refractories [19]. It also should be noticed that the generated B2O3 at high
temperature exists in liquid phase can promote the nucleation of SiC nano particles
[23]. These particles can further growth into SiC fibers under suitable conditions. At
present, the formation process of SiC fiber is interpreted to two mechanisms [24]: the
vapor-liquid-solid (VLS) process and vapor-solid (VS) process. The VLS process
involves vapor transport to a liquid catalyst (Cu, Ni, La et al) [25-27] located at tip of
fibers. The VS process mainly composes of two stages: the nucleation of SiC nano
particles at first and then VS reactions at the tip of fibers. Zhan et al. [28] found that
Ni-Si-C-O liquid droplet was formed by dissolution of Si (g), SiO (g) and CO into Ni
particles at high temperature. SiC nucleus could formed when Si and C were
oversaturated in the droplet, thus facilitating the SiC fibers formation at initial stage.
At present, a systematic work about the effect of B4C on the properties and
microstructure of ASC castable refractories has not been reported. In this paper, the
effect of different addition of B4C on the properties of ASC castable refractories were
studied, the microstructure of non-oxidized areas of samples were analyzed by X-ray
diffraction (XRD) and scanning electron microscope (SEM), the in-situ formed SiC
fibers were characterized by transmission electron microscope (TEM).

2. Experimental procedures
2.1. Raw materials
The raw materials used in the study were brown alumina with different particle
grades (D ≤ 8mm, ≥ 95 wt% Al2O3), silicon carbide (1-0 mm and ≤0.075 mm, 98 wt%
SiC), white fused alumina (99 wt% Al2O3), α-Al2O3 powder (99 wt% Al2O3), ball
pitch (66 wt% C), metallic of Al and Si, B4C (6.5 μm), and calcium aluminate cement
as binder.
2.2. Preparation of ASC castables
Five ASC castable refractories with different addition of B4C (0 wt%, 0.5 wt%, 1
wt%, 1.5 wt%, 2 wt%) were designed, and the details of composition of ASC castable
samples were listed in Table 1.
All the raw materials were first dry-mixed in a mixer, then 6 wt% of extra water
dissolved with reducer (sodium tripolyphosphate, 0.2 wt% of gross mass) was added
to the dry mixed batches. After 5 minutes of mixing, the mixed batches were cast into
cube-shaped molds with a size of 40 mm × 40 mm × 160 mm on a vibratory table
with 2860 vibration/min and vibration amplitude of ±0.6 mm. Cast samples were kept
moisture within the mold for 48 h, and then dried at 110 °C for 24 h. Finally, samples
were fired in air condition at different temperatures for 3h with the heating rate of
5 °C/min below 800 °C and then 3 °C/min until final temperature.
2.3. Test and characterization methods
The apparent porosity and bulk density were measured by Archimedes Principle.
The linear change rate was test according to ISO 2477: 2005, MOD. The cold
modulus of rupture (CMOR) were measured by KZJ-5 anti-rupture test machine. The
thermal shock resistance of 1450 °C fired samples was measured by the method of
water quenching. The fired samples were heated at 1100 °C for 30 min in air
condition and then put into water at room temperature for 5 min. The samples were
dried at 110 °C and their residual CMOR was tested after one thermal shock cycle.
The phase composition of the samples was analyzed by X-ray diffraction (XRD,
D/MAX2200V). Tungsten Filament SEM (HITACHI SU-1500) supported with
energy dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM:
JSM-6700F ) were applied to characterize microstructures of cross-section of samples.
The morphology of SiC fibers was identified by high-resolution transmission electron
microscopy (HRTEM: 200CX ).
The slag resistance of the 1450 °C fired samples were measured using crucible
method. Samples with size of 50 mm × 50 mm × 50 mm were drilled to make a
cylindrical hole at the center, 6 g blast slag was put into each holes of crucible
samples. Then the samples were fired at 1450 °C for 3 h in air atmosphere. The
sintered crucible samples were cut along the center line after cooling to room
temperature. The chemical composition of slag was provided in Table 2.

3. Results and discussion

3.1. Physical properties of ASC castables with different B4C contents
The apparent porosity and bulk density of prepared ASC castable samples after
treating at different temperatures were shown in Fig. 1. After drying at 110 °C for 24
h, the bulk density value increased with increasing B4C content, and the apparent
porosity value decreased correspondingly. The micro-sized B4C particles could fill the
void between coarse grains, thus making the particle packing of unfired samples
closer to ideal packing density. The oxidation of C from decomposition of B4C and
pitch at oxidized zone could generate porosity. Therefore, apparent porosity of all
samples increased after firing at 1450 °C (Fig. 1(a), (b)). B4C reacted with O2 and CO
preferentially above 450 °C and generated C and B2O3 at non-oxidized zone, and
these phase transformations were coupled with volume expansion [19]. Meanwhile,
the liquid B2O3 could further protect C from being oxidized by air , so the apparent
porosity of samples still decreased with the addition of B4C after treating at 1450 °C.
However, when the addition of B4C was over 1 wt%, the bulk density began to
decrease, which could be attributed to the excessive expansion of volume. The
continual increase of linear change rate with the increasing B4C content also revealed
the continual expansion of volume (Fig. 2).
The CMOR of ASC castable samples after treating at different temperatures are
shown in Fig. 3(a). The CMOR was increased significantly with the addition of B4C
after treating at temperature over 1100 °C. The residual CMOR (CMORre) for samples
after thermal shock test is depicted in Fig. 3(b). The CMORre of sample A had the
lowest value while that of sample D had the largest value. These experimental data
suggested that the CMOR and CMORre of ASC castable samples were obviously
affected by the addition of B4C.
3.2. Corrosion resistance
As can be seen from Fig. 4 and Fig. 5, the penetration depth was found to firstly
decrease and then increase with the increasing of B4C. The decomposition of B4C
could generate more carbon. Carbon existed in the micropores could enhance the
corrosion resistance because it has the advantage of nonwettability by molten slag.
The phase diagram of B2O3-Al2O3 from FToxid-FACT oxide databases was given in
Fig. 6, which revealed that the liquid B2O3 could react with corundum, resulting in
(Al2O3)x(B2O3)y formation. These (Al2O3)x(B2O3)y could finally transform into
(Al2O3)9(B2O3)2 with high melt because Al2O3 was enough in the matrix of samples.
The generation of (Al2O3)9(B2O3)2 could decrease micro-pore size and improve the
viscosity of slag during penetration, thus preventing the corrosion of slag. However,
too much fluid liquid generated within the refractories could lower slag penetration
resistance, therefore, the slag penetration depth increased again when the addition of
B4C was up to 2 wt% [29].
3.3. XRD patterns of center zone of samples
The XRD patterns (Fig. 8) at center zone of sample A and sample E after firing at
1450 °C revealed that center zone of sample A and sample E were well protected, and
the SiC at center zone was not oxidized by outside air. A small peak at 2θ = 33.6°
resulted from stacking faults on the (111) plane in β-SiC [30]. Additionally,
other crystal forms of SiC could also be found in Fig. 8 (b).
3.4. Microstructure
The SEM images at the non-oxidized zone of samples with different addition of
B4C (Sample A, C and E) after firing at 1450 °C for 3 h were shown in Fig. 8. Some
gathered carbon balls could be seen at the center zone of sample A in Fig. 8 (a), and
these balls were originated from carbonization of pitch vapor at high temperature.
Interestingly, a large number of slender fibers distributed in the pores at the
non-oxidized zone of samples with the addition of B4C (Fig. 8(b), (c)). The more B4C
added, the more fibers could be observed. This phenomenon implied that B4C could
facilitate the formation of fibers. Their diameters varied from 50 to 200 nm, and their
lengths were from 10 to 50 µm. EDS analysis (Fig. 9(b)) confirmed that these fibers
were mainly composed of C and Si with automatic ratio about 1:1, revealing that the
fibers were SiC fibers. In addition, the other elements derived from the surrounding
matrix. As previously mentioned, the CMOR increased dramatically with increasing
B4C content after firing at 1450 °C. The in-situ generated fibers could play an
important role in the increasing of CMOR and CMORre due to the the crack deflection,
bridging, and pullout mechanisms of fibers [31]. However, too much liquid existed in
the matrix could decrease the thermal shock performance because a sudden change of
B2O3 from liquid to solid can deteriorate the microstructure and strength. Therefore,
CMORre of samples decreased when the addition of B4C was excessive (Fig. 3(b)).
In order to further figure out the effect of B4C on the formation of SiC fibers,
micostructures of non-oxidized zone of sample E and castable sample with 4 wt%
addition of B2O3 fired at different temperatures were investigated. No fibers but B2O3
layer covered on the matrix were observed in the sample with the addition of B2O3 at
900 °C (Fig. 10(a)). However, lots of short rod-like SiC can be observed at 1000 °C.
These rods were longer and more obvious to seen at 1100 °C (Fig.10(e)). This change
presented that the nucleation of SiC particles started at about 1000 °C, and then the
growth of SiC fibers happened at higher temperature when Si (g), CO, SiO (g) were
sufficient in the matrix of samples [10]. A great amount of SiC fibers occupied at
non-oxidized zone of sample E at 1100 °C, but few fibers were generated at lower
temperature, due to the decomposition of B4C at about 1100 °C, which provided
favorable sites and carbon sources for the nucleation of SiC particles and growth of
fibers. Therefore, CMOR of samples with addition of B4C after firing at 1100 °C
increased dramatically due to the in-situ formation of SiC fibers (Fig.3(a)).
3.5. Morphology of SiC fibers
The morphology of fibers was further characterized by TEM and HRTEM in
detail. The TEM photos and corresponding selected area electron diffraction (SAED)
pattern of the marked area were shown in Fig. 11. From the images, the nanofiber had
a rough surface with a diameter of about 50 nm. The corresponding SAED patterns of
part A and part B in Fig. 11(a) were shown in Fig. 11(b) and (c), respectively. Single
β-SiC crystalline phase could be found at a small part of fibers (part A). SAED pattern
of part B (Fig. 11(c)) only showed some featureless streaks and spots that were typical
of a disordered layer structure, and they were also composed of strong twin spots. SiC
polytype with a stacking fault has a lower energy than SiC without stacking faults
[32], therefore, SiC fibers with stacking faults are easily to produce at high
temperature.
HRTEM image of SiC fibers was shown in Fig. 11(d). It can be seen from the
image that the part A showed periodic lattice structure and the marked interplanar
d-spacing was 0.25 nm, which matched with (111) plane of β-SiC and SAED pattern
(Fig. 11(b)).However, part B exhibited a stepped twin structure perpendicular to the
growth direction of fibers.
3.6. Growth mechanism of SiC fibers
In the present study, no clues of liquid globules on tips of fibers were detected by
SEM (Fig. 8(b), (c), Fig. 9(a), Fig. 10(e), (f)) in the in-situ formed SiC fibers,
revealing that the growth mechanism of SiC fibers might not depend on VLS
mechanism but VS mechanism. Based on HSC 6.0 Chemistry software,
thermodynamic calculations for the growth mechanism of SiC fibers were conducted.
In our experiment, the possible reactions related to the formation of fibers in the
system were shown as Eqs. (1)-(7) in Table 3.
During the sintering process, B4C could easily decompose and form the B2O3
(Eqs. (1)), which existed in the form of droplets at high temperature, because of its
low melting point (453 °C). Therefore, the VLS base-growth mechanism might play
an important role in the nucleation of SiC [28]. The more B4C added, the more liquid
B2O3 generated, so more favorable sites for the nucleation of SiC were provided. The
latter process after nucleation of the SiC might be determined by VS mechanism. The
oxygen partial pressure at the edge zone of samples was approximately 0.21 atm. At
the non-oxidized zone, the oxygen partial pressure decreased linearly due to the
oxidization of Si, B4C, SiC, Al, ball pitch [33]. A predominance area diagram for the
system Si-O-C was depicted in Fig. 12 for 1100 °C which revealed that SiC is stable
when the oxygen partial pressure is less than 1 × 10-25 atm. Additionally, Si reacts with
CO and generates SiC when the CO partial pressure is high enough. It is consistent
with the reaction of Eqs. (7). Many articles have reported that the VS generation of
SiC fibers might depend on Eqs. (6) [34-37]. However, ΔGθ of Eqs. (6)
at standard state is greater than zero when the temperature is over 1190 K, which
means that the SiC fibers may generate according to Eqs. (6) only at lower
temperature. In this system, the formation of fibers were likely to predominate by Eqs.
(7) at 1450 °C. The Si and CO gas diffused along the micro-channels in the matrix
and reacted to form SiC at the tip of fibers via a layer by layer deposition. Due to the
variational deposition rate [38] and furnace temperature during growth of fibers, the
twin structure in Fig. 11(d) can be observed.

4. Conclusion
The bulk density of samples after firing at 1450 °C decreased when the addition
of B4C was over 1 wt%. Sample with 1.5 wt% of B4C had the best anti-slag
performance and thermal shock resistance. Excessive addition of B4C could generate
much fluid liquid in the matrix, so less than 1.5 wt% addition of B4C was suggested.
The SiC fibers were formed in the non-oxidized zone of ASC castable refractories
with addition of B4C after firing at 1450 °C in air condition. The obtained fibers
rooted in the walls of inner micropores of non-oxidized zone of samples with the
diameter of 50-200 nm, and the lengths of 10-50 μm. The in-situ formed SiC fibers
played a significant role in the improvement of CMOR of samples after firing at
temperature over 1100 °C. The nucleation of SiC started at about 1000 °C, and then
the growth of SiC fibers happened at higher temperature in a favorable
atmosphere.The thermodynamic calculations revealed that the growth of SiC fibers
mainly according to equation of Si(g)+2CO(g)=SiC(s)+CO2(g) at 1450 °C.

Acknowledgments
The work is supported by Industry-Study-Research Projects of Science and
Technology Commission of Baoshan District, Shanghai, China (bkw2014134). The
authors also wish to express thanks to Pengfei Hu for the valuable discussion.

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Tables
Table 1 Formulation of testing samples (wt%)
Composition A B C D E

Brown fused alumina 67 66.5 66 65.5 65

aggregate
Silicon carbide 17 17 17 17 17
Ball pitch 3 3 3 3 3
Calcium aluminate cement 3 3 3 3 3
White fused alumina 2 2 2 2 2
powder
α-Al2O3 powder 3 3 3 3 3
Metallic Al 2 2 2 2 2
Metallic Si 3 3 3 3 3
B4C 0 0.5 1 1.5 2

Table 2 Chemical composition of blast furnace slag (wt%)

Fe2O3 SiO2 CaO Al2O3 ZnO SO2 MgO others
39.20 29.44 11.01 7.89 7.83 3.98 1.89 4.79

Table 3 Reactions and related Gibbs free energy at standard state

No. Chemical reaction Gibbs free energy at standard state (J) Temperature (K)

(1) B4C(s)+3O2(g)=2B2O3(l)+C(s) ΔGθ= -2394418+419.864T 723-1800

(2) C(s)+0.5O2(g)=CO(g) ΔGθ= -112829-87.859T 723-1800

(3) SiC(s)+Si(s)+O2(g)=2SiO(g)+C(s) ΔGθ= -135944-173.697T 300-1685

(4) Si(s)+0.5O2(g)=SiO(g) ΔGθ= -103965-82.764T 300-1685
 (5) C(s)+CO2(g)=2CO(g) ΔGθ=161470-168.699T 300-1800

(6) SiO(g)+3CO(g)=SiC(s)+2CO2(g) ΔGθ= -418727+351.628T 300-1800

θ
(7) Si(g)+2CO(g)=SiC(s)+CO2(g) ΔG = -689098+329.408T 300-1685

Figures
 Fig. 1. Apparent porosity and bulk density of the ASC castable samples: (a)
110 °C and (b) 1450 °C.

Fig. 2. Linear change rate of the ASC castable samples after firing at 1450 °C.
 Fig. 3. CMOR (a) of the ASC castable samples after treating at different
temperature and the residual CMOR (b) for samples after thermal shock test.
 Fig. 4. Photographs of the crucible cross-sections morphology after slag
corrosion at 1450℃ for 3h. (a): 0 wt% B4C, (b): 0.5 wt% B4C, (c): 1 wt% B4C, (d): 1.5
wt% B4C, (e): 2 wt % B4C.

Fig. 5. The penetration depths at the bottom of crucibles of all samples.

 Fig. 6. Phase diagram of B2O3-Al2O3.

Fig. 7. XRD patterns of center zone of samples after firing at 1450 °C. (a):
sample A, (b): sample E.
Fig. 8. Typical microstructures of the non-oxidized zone of sample A: (a), sample
C: (b) and sample E: (c).
Fig. 9. High-magnification SEM image (a) of fibers in Fig. 7 and corresponding
EDS spectrum of fibers (b).
Fig. 10. SEM images of non-oxidized zone of different samples fired at 900 °C ((a),
(b)), 1000 °C ((c), (d)), 1100 °C ((e), (f)).
Fig. 11. TEM image and corresponding SAED patterns, HRTEM image
of the SiC fibers.

Fig. 12. Predominance diagram for Si-O-C system at 1100 °C.