Preparation and characterisation of

self-flowing refractory material containing

971U type microsilica
nlu*1, A. Odabas1, L. Sezer1, F. Cnar2, S. Guner3, G. Goller1 and
C. Gogtas1, N. U
N. Eruslu1
A newer composition of self-flowing low cement brown fused alumina castable containing 971U
type microsilica was developed. Optimum flow characteristics were achieved using water
addition of 4?6 wt-%. This batch was sintered at different firing temperatures up to 1500uC. To
understand the effect of both firing temperatures and corresponding phases, the present
castable was characterised in terms of X-ray diffraction, scanning electron microscopy, bulk
density (BD), apparent porosity (AP), water absorption (WA), cold crushing strength (CCS) and
self-leveling flowability. The results revealed that gradual increase in firing temperature from 1100
through 1500uC caused low AP and WA, and high CCS properties due to the densification of the
castable.
Keywords: Refractory material, Alumina castable, Firing temperature, Microsilica, Characterisation, Self-flowing

Introduction
Improvements in refractory materials have significant
effect on the most of scientific and technological
developments of the past 100 years, especially on
iron and steel industry, petrochemical and other
industries.13 Over the last three decades, achieving
uniform microstructure with low porosity, high strength
and lower cement content has led the classification of the
refractory castables, as the following, conventional
castable (CaO.2?5%), low cement castable (2?5%.
CaO.1?0%), ultralow cement castable (1?0%.CaO.
0?2%) and cement free castable (CaO,0?2%).1,4,5 Beside
these developments, self-flowing refractory castables
(SFCs) with a consistency after mixing that allows them
to flow and degas without application of vibration, have
joined into the family of refractory castables.58
Successful self-flowability and castable packing density
in refractory castables have been attributed to existency
of the fine particles (fillers) in appropriate amounts.911
Although the benefits (i.e. high mechanical strength,
creep resistance and thermal shock properties) of the
well known refractory castable filler, microsilica (silica
fume) have been evaluated by several researchers,12 the
development of new type microsilica filler, therefore,

Materials Science and Metallurgical Engineering Department, Faculty of

Chemistry-Metallurgy, Istanbul Technical University, 34469 Maslak,
Istanbul, Turkey
2
Istanbul Technical University, Prof. Dr. Adnan Tekin High Technological
Ceramics and Composites Research Center, 34469, Maslak, Istanbul,
Turkey
3
Refsan Refrakter ve Insaat Ltd. Sirketi, Sultan Selim Cad. Ucar Sok.
No. 10/A, 34330, 4. Levent, Istanbul, Turkey
*Correspondence author: necipunlu@yahoo.com

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producing of new type self-flowing refractory castables

with improved flow characteristics are underway. This
study focuses on developing self-flowing brown fused
alumina castable containing 971U-type microsilica.

Experimental
The starting raw materials used in this study and the
composition of the studied refractory castable are listed
in Tables 1 and 2, respectively. Experiments have shown
that 4?6 wt-% water is satisfactory to obtain a selfflowing well dispersed castable system. The preparation
of the castable suspension has been mentioned detailed
in our previous work.13 Flow value measurements were
carried out by pouring the castable suspension into the
truncated flow cone as described in ASTM standard
C230. For the physical tests such as apparent porosity
(AP), bulk density (BD), water absorption (WA) and
cold crushing strength (CCS), the samples were cast by
a simple tapping technique with cube type moulds
(50 mm), then cured for 24 h at room temperature
(25uC). After demoulding, these samples were dried at
110uC for 24 h then fired at different temperatures
(1000, 1200 and 1500uC) for 2 h and furnace cooled. The
apparent porosity (AP), bulk density (BD), and water
absorption (WA) of the samples were determined
according to DIN 51056. The cold crushing strength
(CCS) was measured by a Naber Model press according
to DIN 51067. Seven samples were tested for each
different temperature and their standard deviations were
calculated. After the cold crushing tests (CCS), the
evaluation of the phase formation of the castable
samples was determined by X-ray diffraction (XRD)
analysis. The fractured samples (Fig. 1) were crushed
and sieved under 90 mm for XRD analysis. A
2010 Institute of Materials, Minerals and Mining
Published by Maney on behalf of the Institute
Received 4 December 2008; accepted 8 March 2009
DOI 10.1179/174367609X422199

Go g tas et al.

Preparation and characterisation of self-flowing refractory material

a 110uC for 24 h; b 1000uC for 2 h; c 1200uC for 2 h; d 1500uC for 2 h

1 Castable samples after CCS tests

Panalytical X-Pert Pro model diffractometer with Ni

filtered Cu Ka radiation and a scanning 2h between 10u
and 80u were used. The fracture surfaces of the castable
samples were investigated using the field emission
scanning electron microscopy JEOL JSM 7000F with
fully computer controlled with energy dispersive spectrometry (EDS), wavelength dispersive spectrometry,
electron backscattered diffraction attachments.

Results and discussion

Figure 2 shows the XRD results of the studied castables
at different firing temperatures between 110 and 1500uC.
As shown in Fig. 2a, the castable dried at 110uC for 24 h
consists of corundum (Al2O3, a rhombohedral structure
with lattice parameters a5b50?4758 nm, c51?2991 nm,
PDF no. 100173).14 This result indicates the excess of
alumina in the present castable composition. In addition
to the phases of the corundum observed at 110uC
(Fig. 2a), one silicon oxide phase (SiO2, a cubic structure
with lattice parameters a5b5c50?713 nm, PDF
no. 270605),15 and the phases of albite [Na(Si3Al)O8, a
triclinic structure with lattice parameters a50?8165 nm,
b51?2872 nm, c50?7111 nm, PDF no. 100393],16
anorthite (CaAl2Si2O8, a triclinic structure with
lattice parameters a50?81756 nm, b51?2872 nm, c5
1?41827 nm, PDF no. 411486)17 were detected from the
XRD pattern of the castable sample fired at 1000uC for
2 h, as seen in Fig. 2b. It should be mentioned here that

since both anorthite and albite phases have same crystal

structure with the lattice parameters very close to each
other, the respective X-ray peaks for both phases are
coincident with each other. Observing one diffraction
peak of the silicon oxide indicates a minor content of
cristobalite. This belongs to the devitrification process of
microsilica particles starting about 1075uC, as reported
by Chakravorty and Ghosh.18 When the firing temperature increases from 1000 to 1200uC, the peak intensity of
silicon oxide decreases, and there is no trace indicating
the formation of mullite phase, as shown in Fig. 2c.
However, the diffraction peak of silicon oxide disappeared at 1500uC (Fig. 2d). In addition to the similar
Table 2 Composition
castable

and

self-owability

of

Components

Amount, wt-%

Brown fused alumina

35 mm
13 mm
01 mm
Calcined alumina HTM 30
Rotary bauxite 00.063 mm
Microsilica 971U
Cement Secar71
Dispersant D7S
Water
Self-flowability

16
27
26
10
9
7
5
0.05
4.6
160

studied

Table 1 Composition of starting raw materials used in this study, wt-%

Components

Brown fused alumina*

Calcined alumina{

Rotary bauxite{

Microsilica1

Cement Secar71"

Al2O3
Fe2O3
TiO2
SiO2
Na2O
K2O
Na2OzK2O
MgO
CaO
H2O

96.25
0.14
2.64
0.90

99.50
0.020
0.006
0.018
0.030

88.30
1.48

0.20.30
0.010.1

9898.40
0.150.20
0.20.30

0.10.20
0.20.30

72.70
,0.3
,0.8

,0.6
,0.3
29.20

*Qing dao Asian Minerals Co. Ltd, China.

{Eczacibasi Doga Madencilik San. Tic. A.S. Turkey.
{Qing dao Asian Minerals Co. Ltd, China.
1Elkem Refractories, Norway.
"Lafarge, France.

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Preparation and characterisation of self-flowing refractory material

a 110uC for 24 h; b 1000uC for 2 h; c 1200uC for 2 h; d 1500uC for 2 h

2 X-ray diffraction patterns of castables

diffraction peaks belonging to the corundum, albite and

anorthite as those observed at 1200uC (Fig. 2c), the
measured main peak positions, namely 2h516?4, 33?1,
40?8, 53?9, 70?3 and 74?1u for the XRD scan in Fig. 2d
matched the card values of the mullite (Al6Si2O13, an
orthorhombic structure with lattice parameters
a50?75456 nm, b50?76898 nm, c50?28842 nm, PDF
no. 150776).19 It is considered that the minor content
of silicon oxide has reactioned with corundum from the
matrix and formed mullite at high temperature
(>1400uC). The similar XRD profile has been reported
by Gerotto et al.9,12 who studied the refractory castable
containing 6 wt-% microsilica (MS6).
The microstructural investigation of the fracture
surfaces of the castable samples was performed using
the scanning electron microscope after CCS tests.
Figure 3ad shows the SEM images of the castable
samples dried at 110 for 24 h, and fired at 1000, 1200
and 1500uC for 2 h respectively. The corundum grains
are homogeneously embedded in the castable matrix.
Furthermore, it is clear that increasing the temperature
from 110 through 1500uC reveals the formation of a
dense and compact microstructure of the castable
sample as seen from higher magnification micrographs
given in Fig. 3e and f. The EDS patterns of the points
indicated in Fig. 3a are given in Fig. 3g and h, and
reveal the corundum phase and the average composition
of the matrix respectively.
Self-flowability is the typical characteristic of selfflowing castables, which promotes these mixes autodegasification and flowing without applying external
vibration.20,21 The amount of liquid in a SFC has a

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significant effect on self-flowability, the more liquid in a

SFC, the better its self-flowability.21 However, the excess
water can decrease strength and increase shrinkage,
while less water can cause voids in the castable, consequently poor consolidation and a weak, porous structure.21,22 As given in Table 2, the self-flow behaviour of
the studied castable is 160 where 4?6% water content is
the optimum addition to achieving an acceptable selfflowability property. This value is higher than that of
similar type self-flowing low cement castable containing
920D type microsilica with 5?6 wt-% water addition.13 It
can be seen that the self-flowability is clearly influenced
by the amount of microsilica in the castable. It has been
known that the addition of higher amount of microsilica
in a castable mixture decreases flowability and increases
castable water demand since the microsilica occupies the
cement surface and thereby impedes the dissolution of
the cement.9,23 In addition, comparison of the purity,
consequently, alkalis content in 920D and 971U type
microsilicas24 (SiO2: 92?4 wt-%, H2O: 0?4, LOI:
0?98 wt-% vs SiO2: 98?4 wt-%, H2O: 0?5, LOI:
0?80 wt-% respectively) may indicate that the microsilica
quality has a significant effect on the flow of the
castable. This observation conforms to Mhyre25 who
reported that low purity microsilica significantly
decreases flow and increases water addition in refractory
castable system. Furthermore, it should be noted that
improving the flow and workability related to the some
important well known tips, i.e. achieving properly
dispersed castable matrix, using raw materials with a
rounded particle shape and higher purity alumina,
adding high quality microsilica to the mix, increasing

Go g tas et al.

Preparation and characterisation of self-flowing refractory material

a 110uC; b 1000uC; c 1200uC; d 1500uC; e and f higher magnification micrographs at 110uC and 1500uC, respectively; g
EDS pattern at a specific point A in Fig.3a; h the average composition of the whole matrix in Fig.3a
3 Images (SEM) of the fractural surfaces of castable samples and EDS patterns

the number of coarser grades of alumina used, widening

the particle size range of the formulation.7,11,20,2529
The bulk density (BD) and apparent porosity (AP) of
the studied castable containing 971U type microsilica
were in the range of 3?193?24 g cm23 and 7?1011?25%
respectively. Figure 4 shows the behaviour of both BD
and AP of the castable as a function of the temperature.
The BD of the castable dried at 110uC for 24 h, 3?24
0?03 g cm23, decreases slightly to 3?210?03 g cm23
after firing up to 1200uC, but increases 3?23
0?03 g cm23 at 1500uC. Evaporation of water from the
castable creates porosity, which results in decreased BD

and increased AP (11?250?52%) at 1200uC. The higher

AP observed at 1200uC for the studied castable indicates
that pores obtained during the water evaporation could
not be eliminated, even after firing at higher temperatures (.1000uC). The AP at 110uC, (10?070?27%), is
similar to that of Chakraborty30 who investigated properly designed low cement castables. However, above
1200uC, due to converting most of the metastable liquid
of the castable into the mullite, and the densification of
the composition, the AP significantly decreases to 7?1
0?10% at 1500uC. This kind of decrease of the AP was
reported by Gerotto et al.9 Furthermore, the present AP

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6 Cold crushing strength of castable samples as a function of ring temperature

4 Densication behaviour of castable samples as a function of ring temperature

value is smaller than that of the authors previous

work13 on similar type brown fused alumina castable
containing 920D type microsilica. Therefore, it is clear
that several factors such as total water content, initial
packing density (or porosity), consequently, the grain
size distribution, and the both amount and quality of the
microsilica have significant effects on densification
characteristics of the self-flowing low cement castables.
Figure 5 shows the relationship between the densification characteristic of the castable and firing temperature,
also verifies the behaviour of both the AP and BD given
in Fig. 4. It appears that the WA increases gradually
from 3?100?10% at 110uC to 3?510?20% at 1200uC,
but decreases to 2?230?06% at 1500uC. Furthermore,
the WA value (2?230?06%) of the present castable
sample at 1500uC is similar to the WA value (y2?0%) of
the self-flow ultralow cement high alumina castable
containing 5 wt-% of microsilica.31
Figure 6 presents the cold crushing strength (CCS) of
the castable samples as a function of the firing temperature. The increase in CCS is observed from 924
18 kg cm22 for 110uC dried samples to 1784
160 kg cm22 for the samples fired at 1500uC. The
castable sample, dried at 110uC for 24 h, is about 0?5
times stronger than the similar type brown fused

alumina castable containing 920D type microsilica, it

is also close to that of the self-leveling cement tabular
alumina castable with 4?7% water addition.32 Furthermore, the present CCS values are significantly higher
than those of a lightweight low cement self-flowing
castable,33 i.e. 92418 kg cm22 for 110uC and 1072
46 kg cm22 vs 296 kg cm22 at 110uC and 887 kg cm22
at 1000uC. The mechanical characteristics of ceramic
systems containing high alumina contents are related to
the phase formation (i.e. amount of corundum, a glassy
phase composition, etc.) and microstructure (crystal
size, and shape, a glassy phase and secondary crystalline
phase distribution, porosity, etc.).34,35 As seen in Fig. 2b
and c, the anorthite, albite, and minor silicon oxide
phases crystallise and gradual increase observed in CCS
indicates the ceramic bond formation. After firing at
1500uC for 2 h, the castable exhibits the highest value of
the CCS due to not only the enhanced densification, but
also the formation of elongated needle shaped mullite
crystals which strengthens the structure at high heat
treatment temperatures.36

Conclusions
In the present investigation, the authors have prepared a
self-flowing low cement brown fused alumina based
refractory castable containing 971U type microsilica.
Water addition (4?6%) has been used to achieve full selfflowing characteristics. The castable sample self-flowed
under its own weight and easily filled intricate shaped
moulds without any vibration. At 110uC, the matrix
consists of corundum phase. With increasing firing
temperature through 1200uC, the phases of corundum,
anorthite, albite and silicon oxide were detected. At
1500uC, the mullite formation was observed due to the
reaction of silicon oxide with corundum. The investigated physicomechanical characteristics exhibited that
several factors such as total water content, initial
packing density (or porosity), therefore, the grain size
distribution, and both amount and quality of the
microsilica have significant effects on densification
property of the self-flowing low cement castables.

Acknowledgements
5 Water absorption of castable samples as a function of
ring temperature

10

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This work was financially supported by the Istanbul

Technical University, Turkey, Research Fund (Project

Go g tas et al.

nlu would like to thank Professor

No. 30329). N. U
Mohan J. Edirisinghe for his helpful discussion. The
authors wish to thank Mr Huseyin Sezer for his help and
contributions during the SEM analysis of this study.

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