Refractories Manual 2/2012 107

Special technologies

R. Sarkar*, A. Mishra*

High-Alumina Self-Flow Castable with

Different Cement Binders
The author Abstract Keywords

The corresponding author, Dr. Ritwik Sarkar, Asso-
ciate Professor, NIT, Rourkela, India, has about 15
years of experience in ceramics and refractories. He
has work experience with IFGL Refractories Ltd., IF-
GL Bioceramics Ltd., CG & CRI, R&D of ACC Ltd.,
and H&R Johnson Ltd., all in India, and at the IKKM,
RWTH Aachen, Germany (DAAD Fellowship). Dr.
Sarkar has received many awards in his career for
academic excellence and his contributions to Ceramics and Materials
Science, including the Young Scientist Award. A life member of the In-
dian Ceramic Society & Indian Institute of Ceramics, Dr. Sarkar has
more than 80 research publications and 9 patents to his credit. E-Mail:
ritwiksarkar@rediffmail.com
A high-alumina self-flow castable was de- alumina castable,
veloped with a distribution coefficient self flow, cement,
q=0.21 (Dinger–Funk’s continuous particle properties
size distribution model) using two different Refractories Manual
types of high-alumina cements at an amount 2012 [2]
of 4 and 6 mass-%. Castable compositions
were processed as per conventional pro-
cessing techniques and self-flowing charac-
teristics were obtained using a maximum
water content of 5.2 %. All compositions
were studied for their flowability and various
properties under dried and fired conditions

1 Introduction
The ever-increasing demand and applica-
tion of unshaped refractories to replace con-
ventionally shaped refractories due to many
major advantages [1] have inspired scien-
tists and manufacturers to continuously in-
vestigate these materials in depth and to im-
prove their quality and performance. Since
the early 1960s, the availability of purer cal-
cium aluminate cements (CACs) with high-
er alumina content has made the unshaped
refractory system purer allowing their use in
various high-temperature applications [2].
Among the various unshaped refractories,
castables lead in all the areas of research, de-
velopment, manufacturing, and application.
Physical, mechanical, chemical, and ther-
mo-mechanical characteristics of various
castable systems as well as their processing
and bonding mechanisms are the focus of
such investigations.
Refractory castables are combinations of re-
fractory aggregates, matrix components,
bonding agents, and additives. The propor-
tions of each component used vary in each
castable composition to achieve the desired
properties essentially required for the in-
tended application. Among different bond-
ing agents calcium aluminate cement is the
* Depart. of Ceramic Engineering,
National Institute of Technology,
Rourkela - 769008, Orissa, (India)
commonly used hydraulic binder in refrac-
tory castable compositions, but the presence
of CaO in the cement results in low melting
phases with Al2O3 and Al2O3-SiO2 refracto-
ry systems [1, 2]. Other important concerns
for cement-containing castables are the cur-
ing and dewatering steps, which must be
carefully conducted in order to reduce ex-
plosive spalling [1]. A significant increase in
the life and performance of alumina-based
castables has been made possible by de-
creasing the cement content, thus avoiding /
reducing the chances of explosive spalling
and the formation of a liquid phase at appli-
cation temperatures, which in turn improves
the corrosion resistance and creep strength
[3–5].
Again flowability of the castables is very im-
portant for application purposes and their
final performance. Better flow of any casta-
ble allows one to make a good lining and
makes it possible to line an intricate shape.
In this regard self-flowing castables are the
best as no external energy is required to flow
the castable, it can flow under its own weight
and the best lining performances may be ex-
pected from these self-flowing castables.
This flowability is dependent on the particle
size distribution and packing of the castable
system.
The particle packing in refractories can be
divided into two categories, namely, discrete
packing and continuous packing. In mono-
lithics, the type of packing plays a vital role.
Furnas [6] stated that maximum packing
density is obtained when particles of smaller
size fill the voids between particles of great-
er size. According to Andreassen’s model
[7–9] particles cannot be of a particular size
instead they come within a certain narrow
size range. The cumulative percent finer
than (CPFT) according to Andreassen’s
model is given by
CPFT = (d/D)q x 100 (1)
where d is the particle size for which CPFT
is being calculated, D is maximum particle
size, and q is distribution coefficient.
The drawbacks of Andreassen’s model are
that he did not assume any specific mini-
mum particle size and assumed that the par-
ticles can be infinitesimally small which is
practically not possible. So this model was
modified by Dinger and Funk [10] who con-
sidered a specific minimum size of particles
to make the model more acceptable. The
CPFT according to Dinger and Funk’s mod-
el is as follows
CPFT = ((Dq–Dminq)/(Dmaxq–Dminq)) x 100
(2)
where D is the particle size for which CPFT
is being calculated, Dmin is the minimum
particle size, Dmax is the maximum particle
108 Refractories Manual 2/2012

Special technologies

1 cured, dried, and fired. Various properties

of the castables were studied for a compara-
100 tive understanding of the effect of addition
of the two different cements.
90

80 2 Experimental
High-alumina self-flow castables were pre-
70 pared using white tabular alumina (WTA)
(Almatis, India), white fused alumina
60
(WFA), and brown fused alumina (BFA)
CPFT / %

50
(both from Orient abrasives, India) grains/
aggregates, technical alumina fines (Indal,
40 India), two different high-alumina cements
namely cement 1 (Almatis, India) and ce-
30
ment 2 (Polychem, India), silica fume
20
(Elkem, India) and additives like defloccu-
lants and set retarder. Details of the physico-
10 chemical properties of the starting materials
are provided in Table 1. The continuous par-
0
0.0025 0.15 0.3 0.5 1 2 3 6
ticle size distribution model as proposed by
Particle Size / mm Dinger and Funk [10] was used for the cast-
Fig. 1 • Plot of CPFT able system with a distribution coefficient
against particle size (q value) of 0.21, using the coarsest particle
size of 6 mm and finest of 0.001 mm. Table 2
shows the cumulative percent finer than
size, and q is the distribution coefficient. ferent percentages in a high-alumina self- (CPFT) of different particles sizes and Table
Various works on castable formulations are flow castable having a distribution coeffi- 3 shows the percentages of the different par-
based on this Dinger and Funk model. cient (q value) of 0.21. Castable composi- ticle size fractions that are used for making
The present work is designed to compare tions were mixed to attain similar the castable compositions. Four different
two different high-alumina cements, at dif- self-flowing consistency, and then cast, castable batches were prepared using

Table 1 • Physico-chemical properties of the starting materials of castable

Constituents

Technical Fume silica

WTA grain BFA grain WFA grain Cement 1 Cement 2
alumina fines 971 U

Chemical analysis (oxide content in mass-%)

SiO2 0.04 0.4 0.1 0.2 96.1 0.21 0.85

Al2O3 99.4 95.66 98.92 98.0 0.4 71.85 73.13

Fe2O3 0.04 0.4 0.06 0.06 0.1 0.11 0.28

TiO2 0.64 trace 0.11

CaO 0.01 0.2 26.92 24.15

MgO 0.1 0.23 0.45

Na2O + K2O 0.16 0.08 0.34 0.4 0.22 0.51

Loss on Ignition 0.2 0.9 0.31 0.35

Physical properties

Avg. size / µm 1−3 <45

Bulk density / g/cm3 3.61 3.83 3.77

App. porosity 3.92 % 1.7 % 1.8 %

Spec. surface
~20 4500 4300
area / m2/gm
CA 2* CA2
Phase analysis corundum corundum corundum corundum amorphous
CA** CA
*CaO 2Al2O3, **CaO Al2O3

2 3
Fig. 2 • Variation of bulk density against temperature
4 mass-% and 6 mass-% of cements of two
different varieties. Other than binder silica
fume at an amount of 4 %, dispersant (sodi-
um poly-metha acrylate) at an amount of
0.1 %, citric acid 0.05 %, and organic fiber
0.05 % were used. The batch compositions
are given in Table 4. All the batches were
processed under similar conditions.
First, all the raw materials were dry mixed
in a planetary mixer (Hobart, UK, model
N50), water was added till the mix attains
self-flowing consistency. Mixed composi-
tions were characterized for self-flowability,
using a flow cup, as per Fang and others
[14]. Water-mixed castable compositions
were placed in the cup and after 30 s the ma-
terial was allowed to flow onto a flow table
(without vibration) by drawing the cup up-
ward. Measurement of flow was done after
allowing the material to flow (spread) for
120 s. Flow values (an average of eight dif-
ferent directions for each composition) are
represented along with the water require-
ment in Table 5.
Table 2 • CPFT for various particle sizes with
distribution coefficient q=0.21
Particle size / mm CPFT / mass-%
6 100
3 83.2
2 74.4
1 61.2
0.5 49.6
0.3 42
0.150 33
0.001 0 0.001
RefRactoRies Manual 2/2012
Special technologieS
Fig. 3 • Variation of cold crushing strength against temperature
Next the mixed batches were poured into lu-
bricated molds of dimension 50 mm3. The
excess mix was scraped off and smoothened
by a trowel. The mixes were allowed to age
for 24 h inside the mold under humid con-
ditions. Next they were de-molded and al-
lowed to air dry for 24 h followed by oven
drying at 110 °C for 24 h. The dried samples
were then fired at 1000 °C and 1600 °C with
2 h soaking time at peak temperatures.
Dried and fired cubes were characterized
for volumetric shrinkage, bulk density (BD),
and cold crushing strength (CCS) (all mea-
sured as per Bureau of Indian Standard
(BIS) specifications, IS 1528 – 1974, Part
XII, Part VIII and Part IV, reaffirmed in
2002). All data represented here are an aver-
age of five individual measurements. Six
weight percent cement containing 1600 °C
fired samples were tested for phase analysis
by the X-ray diffraction method.
Chemical analyses of the starting raw mate-
rials were conducted using the acid-dissolu-
tion method. Densification studies were
Table 3 • Percentage aggregate for each
fraction
Particle size range / Percentage
mm (mass-%)
–6 to +3 16.8
–3 to +2 8.8
–2 to +1 13.2
–1 to + 0.5 11.6
–0.5 to +0.3 7.6
–0.3 to +0.15 9 that of the 4 % cement-containing composi-
–0.15 to +0.001 33
0
109
conducted using the conventional liquid-
displacement method according to the Ar-
chimedes principle. Phase identification was
performed with an X-ray diffractometer
(PW-1830, Philips, Netherlands) using
Cu-Kα radiation with a scanning speed of
2 °/min. Firings were conducted in a
programmable electric furnace (Bysakh &
Co., India). Cold crushing strength was
measured in a compressive testing machine
(AIMIL, India).
3 Results and discussion
Two different cements were found to be
very close in terms of characteristics, except
for the chemical constituents. Cement 2 has
a little higher alumina content and corre-
spondingly a little lower lime content com-
pared to Cement 1. Figure 1 shows the plot
of CPFT against particle size for the distri-
bution coefficient q=0.21. The highest par-
ticle size of 6 mm has a CPFT of 100 % and
the lowest particle size of 1 µm shows 0 %
CPFT. There is an abrupt change in the
slope of the plot in the finer size range due
to the high fine content (33 %) in the com-
positions (low q value). The fines mainly
consist of technical alumina fines, cement,
and fume silica.
Table 5 shows the water requirement of cast-
ing and the flow value. A self-flowing nature
was obtained even at a maximum water con-
tent of 5.2 %. 6 % cement-containing com-
positions required a greater amount of water
to attain a self-flowing consistency and also
resulted in lower flow values compared to
tion. This may be due to the higher amount
of lime (cement) present causing an in-
creased hydration reaction in the presence
110 RefRactoRies Manual 2/2012

Special technologieS

4 ment 1 containing ones. This greater extent

of densification of 4C2 and 6C2 composi-
tions was because of the presence of the
higher extent of impurity phases in cement
2, as observed in the chemical analysis
(Table 1).

3.2 Cold crushing strength study

Figure 3 shows the variation of the cold
crushing strength (CCS) values of different
castable compositions against firing tem-
perature. Degradation of strength at inter-
mediate temperature due to the breakage of
hydraulic bonds in cement-containing cast-
able was not very significant for all the com-
positions. A higher amount of cement of
both types showed greater values of CCS for
all the firing temperatures. However, ce-
Fig. 4 • XRD plot ment 2 showed relatively lower strength val-
and peak list of 6C1 ues for all conditions. Castables fired at
composition fired 1600 °C showed reasonably very high
at 1600 °C strength values for all compositions,
which is associated with the densification
of the products.
of water, demanding a greater amount of cement showed little higher density values
water and the resultant hydraulic products for all temperatures. Reduction in BD val- 3.3 Phase analysis of 1600 °C fired casta-
degrade the flow values. ues was not observed on increasing the fir- bles
ing temperature from 110 to 1000 °C due to Phase analysis by XRD of the 6 % cement-
3.1 Bulk density study breakage of hydraulic bonds. The increase containing castables fired at 1600 °C
Figure 2 shows the variation in bulk density in density values upon further increasing resulted in similar characteristics in both
(BD) of the different compositions studied temperatures was caused by the sintering the cement types. Corundum is found as
against firing temperature. All the castable of the compositions. The slope of density the major phase and grossite (CA2) as the
samples show relatively close BD especially plots for the cement 2 containing 4C2 and minor one for both 6C1 and 6C2 composi-
at 110 and 1000 °C. A higher amount of 6C2 compositions was sharper than the ce- tions. No hibonite phase (CA6) formation
was observed. Again no peak for the calci-
um aluminate (CA) phase was found (which
Table 4 • Batch compositions (in mass-%) of different castable com-
was present in the cements). This may be
positions because of the reaction between fine alumi-
Particle size range / na and the CA phase at high temperatures in
4C1 6C1 4C2 6C2
mm the matrix of the castable increasing the
–6 to + 3 (BFA) 16.8 16.8 16.8 16.8 grossite (CA2) phase. Figure 4 shows the
XRD plot of the 6C1 composition as a repre-
–3 to + 2 (WTA) 8.8 8.8 8.8 8.8
sentative one.
–2 to + 1 (WTA) 13.2 13.2 13.2 13.2
4 Conclusions
–1 to + 0.5 (WFA) 11.6 11.6 11.6 11.6
The effect of different high-alumina ce-
–0.5 to + 0.3 (WTA) 7.6 7.6 7.6 7.6 ments on high-alumina self-flow castables
–0.3 to + 0.15 (WTA) 9 9 9 9
(distribution coefficient q=0.21) was stud-
ied. Good self-flowing properties were ob-
–0.15 to + 0.0025 tained for all compositions using a maxi-
25 23 25 23
(tech. alumina fines)

–0.15 to + 0.0025
4 6 - -
(Cement 1) Table 5 • Water consumption and flow value of different castable com-
–0.15 to + 0.0025 positions
- - 4 6
(Cement 2) Water required for
Composition Flow value / %
casting / %
–0.15 to + 0.0025
4 4 4 4 4C1 4.4 96
(Fume silica)

Dispersant 0.1 0.1 0.1 0.1 4C2 4.6 91

Citric acid 0.05 0.05 0.05 0.05 6C1 5 86

Organic fiber 0.05 0.05 0.05 0.05 6C2 5.2 82

 Refractories Manual 2/2012 111

Special technologies

[2] Banerjee, S.: Recent developments in mono- (1929) [2] 175−179

mum water content of 5.2 %. BD values were
found to increase sharply at higher tempera-
ture and cement 2-containing compositions
showed greater BD values due to sintering
in the presence of the higher extent of impu-
rities in the cement. CCS values did not
show much degradation at intermediate
temperature and reasonably very high
strength was obtained on firing at 1600 °C.
Phase analysis showed only a little grossite
other than the major corundum phase; no
hibonite or calcium aluminate phases were
observed.
References
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[3] Masaryk, J.S.: Development and use of low ce-
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[4] Bhattachariya, K., Chintaiah, P., Chakraborty,
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Received: 18.06.2012

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