R E SE A R CH A N D D E V ELO PM EN T | A LUM I N A C A S TA B L E S

A Study on the Phosphate-Bonded

High-Alumina Castable –
Effect of MgO Addition
R. Sarkar1 , U.K. Behera1
Abstract: Mono-aluminium phosphate [MAP, Al(H2PO 4)3] is a widely used chemical binder in
the refractory industries due to its higher water solubility and greater bonding strength at low
temperatures as it reacts with both basic and amphoteric oxides and has higher application
temperature. In the present work, commercial-grade MAP is used in high-alumina castables,
with different particle size distributions, as the sole binder. The effect of addition of 1 mass-%
MgO as a setting accelerator to the castable compositions is also studied. Castables are processed
as per conventional processing methods and heat treated after drying at 1000 and 1600 °C.
Dried and fired compositions were evaluated for density and strength. Also micro-structural study
of the 1600 °C sintered samples was carried out. Addition of MgO resulted in a marginal decrease
in density values which may be due to a greater amount of hydrated phase formation and their
decomposition at higher temperatures; but it significantly increased crushing strength for all the
heat treatment temperatures. Greater bonding from faster reaction at low temperature and the
formation of a liquid phase at higher temperatures are the reasons for such an enhancement.

Keywords: phosphate bonding, alumina castables, MAP, MgO addition, properties, microstructure

1. Introduction
Refractory castables can be classified as a
blended mixture of different fractions of
refractory aggregates and fines with a
bonding agent and various additives. They
are supplied in dry condition as loose pow-
ders and mixed with a liquid (usually water)
at the user’s industry site and then vibrated,
poured or pumped, or pneumatically shot
into the application area to form the desired
shape or structure that becomes rigid
because of hydraulic or chemical settings
and then fired for densification and
strength development [1]. Applications of
castables have grown significantly in the
last half-century and over the years casta-
bles have changed from simple mixes to
very complex engineered formulations,
used in a variety of very demanding and
critical industrial applications. Also in
many of the applications castables are the
most appropriate choice due to better per-
formance and easier installation [2].
Type of bonding material used and its
amount greatly affect the properties and per-
formances of the castable. The bonding
agent of a castable may change the chemical
composition, fluidity, workability, dry-out,
firing conditions and finally the properties
[3]. Hence much research is available in the
literature to improve the quality of castables
by using different bonding agents [1–9].
Binders are essential for the development of
strength at both ambient and elevated tem-
peratures and also help to retain the shape
under green conditions as no compaction is
involved in the shaping process during
installations of castables. Different bonding
materials commonly used for castables are
hydraulic (cement and hydratable alumina),
chemical (phosphate, silicates, geopolymers,
etc.), colloidal (silica sol, alumina sol) and
others [1, 6–9].
In the case of chemically bonded refrac-
tories, a chemical bond is formed between
the bonding agent material and refractory
constituent that sets the unshaped (casta-
ble) refractory, retains the shape, and pro-
vides strength even up to elevated tempera-
tures. For phosphate bonding, the phos-
phate bond is intentionally developed in the
refractory system. There are plenty of phos-
phate-forming compounds available com-
mercially and among them phosphoric acid
(H 3PO 4) or mono-aluminium phosphate
[MAP or Al(H2PO4)3] are the main bonding
agents that have been widely studied for
refractory castables [10]. According to the
proposed setting mechanism in the litera-
ture [1, 10–12], H3PO4 initially reacts with
Al 2O3 (above 127 °C) or Al(OH)3 at room
temperature forming MAP. This MAP
decomposes on heating to form ortho alu-
minium phosphate (OAP, AlPO 4) till
1327 °C and which on further heating forms
pure alumina and phosphoric pentoxide in
a gaseous state. The details of the equations
are given below. Also, MAP is considered
[8, 13−14] to be the most applied chemical

44 Refractories Manual 2018 www.interceram-review.info

Authors
DR. RITWIK SARKAR
(ritwiksarkar@rediffmail.
com), is Professor, National
Institute of Technology,
Rourkela, India, with more
than 20 years of experi-
ence in Ceramics & Refrac-
tories. He has work experi-
ence in private sectors
like IFGL Refractories Ltd.,
ACC Ltd., H&R Johnson (I)
Ltd., and also in R & D or-
ganization like CSIR-CGCRI
in India and IKKM, RWTH
Aachen, Germany (DAAD
Fellowship). Dr. Sarkar has
received many awards in
his career for his academic
excellence and scientific
contribution in Ceramics &
Materials Science including
Young Scientist Award.
binder in the refractory field due to its high
solubility in water, high bonding strength
and reaction with basic and amphoteric raw
materials at low temperatures, high applica-
tion temperature and no residual impurity
phase in the final product.
Table 1 Physico-chemical properties of the raw materials
(WTA – White Tabular Alumina, WFA – White Fused Alumina) (©R. Sarkar)
Constituent WFA grain [%]
Al 2 O 3 98.93
SiO 2 0.1
Fe 2 O 3 0.06
TiO 2 Trace
CaO 0.1
MgO – –
Na 2 O + K 2 O 0.4
Bulk density [g/cm ] 3
3.77
Apparent porosity [%] 1.8
Specific sur face area [m 2 /g] – –
Phase analysis Corundum
67th Volume
6H3PO4 + Al2O3 = 2Al(H2PO4)3 + 3H2O amount of strength at operating tempera-
(Temperature 127–427 °C) (1) tures above 1300 °C (because of complete
decomposition of phosphate) till the ceramic
3H3PO4 + Al(OH)3 = Al(H2PO4)3 + 3H2O bond forms on sintering. This binder system
(Room temperature) (2) also has a poor ability to bond with existing
fired refractories. In addition, the refractory
Al(H2PO4)3 = AlPO4 + 3H2O + P2O5 lining has a high chance of lamination as
(Temperature 732–1327 °C) (3) they have a weak bonding strength.
An important aspect of phosphate bond-
2AlPO4 = Al2O3 + P2O5 ing is that it takes a long time for setting or
(above 1350 °C) (4) hardening in high-alumina castables at room
temperature [10]. Thus, the soft/plastic char-
So this bonding finally results in pure alu- acter can be retained for a long time in phos-
mina with no trace of phosphorus in the phate-bonded unshaped compositions and
fired composition. Also, phosphate shows they are widely used for plastic refractory
better bonding with metallic parts com- compositions. For castable applications, set-
pared to other bonding systems [1]. But there ting is desired within a specific time period
are several disadvantages associated with and so addition of setting accelerators (i.e.,
phosphates. Primarily the setting of the MgO, CaO, calcium aluminates, etc.) to the
material is very slow and sluggish. In order compositions is required. These additives
to speed up the reaction, setting agents are induce an acid–base reaction, thus a fast set-
used, like, MgO, CaO, calcium aluminates, ting reaction occurs, resulting in the forma-
etc. These additives induce an acid–base tion of phosphate-based salts (amorphous/
reaction, forming amorphous/crystalline crystalline) and the refractory is set with desir-
phosphates that enhance refractory harden- able properties [8, 10]. The phosphate bond is
ing and other properties. Also phosphate mainly important for its good adhesion and
bonding requires considerable amounts of lesser chance of cracking during heating,
mechanical moisture for workability and so allowing faster repair and reduced downtime
a long heat-up schedule is required for dry- [10, 15–16]. However, a detailed study of this
ing. The green strength is weak due to the bond material in the castable system is not
lack of strong bonding, like in cement. On widely available in the literature. Such a study
firing, the bond system loses a considerable is planned in the present work with a high-alu-
mina castable system having two different
particle size distributions and in the presence
of a setting accelerator (MgO).
WTA grain [%] Alumina fines [%]
99.34 99.5 2. Experimental
0.03 0.03 The phosphate-bonded high-alumina casta-
ble was prepared using different grain sizes
0.035 0.03
of white fused alumina (from a Chinese
– Trace source), white tabular alumina (WTA)
– 0.02 (Almatis, Kolkata, India), technical alumina
fines (Almatis, India) and liquid mono-alu-
0.01
minium phosphate (MAP) (Mrk Chemicals,
0.15 0.1 India). The MAP used was a colourless, vis-
3.61 – cous, adhesive solution, with an Al2O3 con-
3.93 – tent ~8–10 %, P2O5 content ~35–38 %, spe-
cific gravity between 1.50–1.55 and a viscos-
2.6
ity at room temperature between 18–25 s
Corundum Corundum (Ford Cup B-4 method). The details of the
physico-chemical properties of the other raw
materials are provided in Table 1. For the
2018 Refractories Manual 45
R E SE A R CH A N D D E V ELO PM EN T | A LUM I N A C A S TA B L E S
batches containing MgO as a setting acceler-
ator, freshly calcined MgO, prepared by cal-
cining chemical-grade magnesium hydrox-
ide (99 % pure, Loba Chemie, India), is added
at an amount of 1 mass-%. The castable com-
positions with different particle size distri-
bution were formulated using a Dinger and
Funk model with distribution coefficients, q
values, of 0.21 and 0.29 [1–7, 20] and the dis-
tribution plot of both the distribution coef-
ficients is provided in Figure 1. Details of the
batch composition are given in Table 2. A
fixed amount of 8 vol-% to mass-% of the
MAP solution was used for the study.
All the raw materials were initially dry-
mixed in a planetary mixer (model N50;
Hobart, Peterborough, UK). First, the
coarser components were mixed, then the
fine components were added (also calcined
MgO for the MgO-containing batches), and
finally, the MAP solution was added. After
proper mixing and a desirable flow consist-
ency was achieved, the whole mixture was
then cast in a lubricated iron mould of 50
mm cube size. The cast specimens were
cured within the mould for one day, and then
they were dried in a hot air oven at 200 °C for
24 h. The dried specimens were fired at 1000
and 1600 °C at the rate of 3 K/min with a
soaking period of 2 h. All the firings were
conducted in a 1700 °C programmable elec-
tric furnace (Okay & Co., India). The dried
and heat-treated specimens were character-
ized for density, strength, phase analysis and
micro-structural study. Density and strength
were characterized as per Bureau of Indian
Table 2 Particle size distribution in the batch of the castable composition (©R. Sarkar)
Components Size [mm]
White Fused Alumina 3–2
White Tabular Alumina 2–1
White Tabular Alumina 1–0.5
White Tabular Alumina 0.5–0.2
White Tabular Alumina 0.2–0.05
Alumina Fines 0.05–0.01
White Tabular Alumina 0.2–0.05
Alumina Fines 0.05–0.01
46 Refractories Manual 2018
Figure 1 Particle size distribution used in this work (©R. Sarkar)
Standard (BIS) specifications, IS 1528–1974, ent work. The highest particle size of 3 mm
reaffirmed on 2002. Each data represented has a CPFT of 100 % and the lowest particle
here are an average of five individual meas- size being 0.01 mm shows 0 % CPFT. The
urements. Micro-structural study of the composition with a q value of 0.21 has a
1600 °C sintered samples was conducted by higher extent of fines content. There is an
a field-emission scanning electron micro- abrupt change in the slope of the plot in the
scope (Nova Nano, FEI, USA) after gold finer size range due to the high fines content
coating through a sputter coater. in the compositions (low q value). Table 2
shows that the percentage of finer (< 0.2 mm)
fraction is greater for the composition q =
3. Results and Discussion 0.21. Physico-chemical properties of the
Figure 1 shows the plot of CPFT (cumulative starting raw materials (Table 1) indicate that
percent finer than) of different size fractions the materials are pure and contain the very
against particle size for the distribution coef- minimum of impurities.
ficients q = 0.21 and 0.29, used for the pres-
3.1 Density Study
Figure 2 shows the variation in bulk density
(BD) of different compositions studied
Mass-% for q = 0.21 Mass-% for q = 0.29 against firing temperature. Density values
were found to increase with the increase in
11.7 13.72
temperature. Also BD was found to increase
17.82 20.02 with the q value. Higher q value means
15.4 16.37 greater extent of coarser fractions, which has
a greater bulk density value than the finer
16.21 16.2
fraction. But addition of MgO was found to
21.49 19.63 reduce the densification of the compositions
marginally for both q values at all tempera-
17.38 14.06
tures. Addition of MgO causes faster reac-
21.49 19.63 tion between basic MgO and acidic phos-
17.38 14.06
phate (MAP) in the composition, resulting in
hydrated magnesium phosphate-based reac-
tion products [10, 12, 21–22].
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Figure 2 Variation in bulk density of the castables (©R. Sarkar)
MgO + 2Al(H2PO4)3 + 9H2O
= Mg(H2PO4)2 ∙ 2H2O + 2(MgHPO4  sitions, is absent as these compositions are
∙ 3H2O) + 2(AlPO4 ∙2H2O)
These reactions occur during the castable
processing steps and the formed Mg(H2PO4)2
∙2H 2O phase is a metastable/soluble com-
pound whereas the MgHPO4∙3H 2O (new-
beryite) phase is a well stable/insoluble one.
These hydrated magnesium phosphate
phases decompose to different anhydrous
magnesium phosphates on heating, namely
Mg 2P 2O7, Mg(PO3)2 and Mg 3(PO 4)2 . The
presence of these hydrated phosphates at low
temperatures (dried condition) and their
decompositions at higher temperatures
causes a decrease in the density values for all
the different temperatures. The MgO-con-
taining compositions resulted in lower den-
sity values compared to that of batches with-
out MgO. However, the effect of temperature
is found to be similar for these batches.
3.2 Strength Study
Figure 3 shows the variation of the cold
crushing strength (CCS) values of different
castable compositions against firing temper-
ature. Strength values are found to increase
with increasing temperatures for all the
castable compositions having different q val-
ues and MgO content. Degradation of
strength at intermediate temperature, com-
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monly found in cement-containing compo-
(5) not based on hydraulic bonding. Castables
with higher q value result in greater strength
which may be associated with greater densi-
fication, associated with compaction [2–3,
25]. Addition of MgO is found to considera-
bly enhance the strength values of the casta-
bles for all temperatures and q values. The
presence of MgO enhances phosphate bond
formation, both by forming Mg-based phos-
phates and also enhancing the Al-based ones
Figure 3 Variation in cold crushing strength of the castables (©R. Sarkar)
by increasing the temperature of the matrix
phase due to the exothermic reaction of
Mg-phosphate formation. Thus, the pres-
ence of MgO at low temperatures enhances
the bonding of the castables, thus enhancing
the strength. Again, at higher temperatures,
the low melting characters of Mg-based
phosphates [such as Mg3(PO4)2 which has
a melting point ~1357 °C and Mg(PO3)2
~1165 °C] produce liquid phase [10] bonding
in the compositions enhancing the strength.
But, as the amount of MgO addition was not
significant, the extent of liquid phase for-
mation was limited and did not degrade
the properties.
3.3 Micro-Structural Study
Figure 4 shows the micro-structural fea-
tures of the different compositions sintered
at 1600  °C. Figure 4 A and C show the
micro-structure of compositions without
MgO and indicate that the composition
with q = 0.21 has lower grain sizes com-
pared to that of q = 0.29. The granular struc-
ture is found to be a non-uniformly com-
pacted one; it is observed to be well com-
pacted in certain portions and not well
compac ted i n ot her por t ions w it h
inter-granular porosities. But the addition
of MgO is found to change the micro-struc-
tural features considerably. Micro-photo-
graphs of both the q values show consider-
able growth of the grains and the sharpness
2018 Refractories Manual 47
R E SE A R CH A N D D E V ELO PM EN T | A LUM I N A C A S TA B L E S

of the grains is reduced. MgO-containing
compositions have relatively rounded
grains indicating the presence of a liquid
phase at 1600 °C sintering. Grains are in
contact with each other which may help in
bonding and increasing strength. However,
the grains are not well compacted ones and
inter-granular porosity is commonly
observed. This liquid phase formation and
grain bonding has helped in increasing the
strength values at room temperature but
may adversely affect the strength values at
high temperatures.
4. Conclusions
MAP-bonded high-alumina castables hav-
ing distribution coefficients (q values) of 0.21
and 0.29 with and without MgO addition
were prepared and processed through con-
ventional castable processing techniques. A
higher q value and temperature resulted in a
higher density but the presence of MgO mar-
ginally reduces the density values which may
be associated with a greater extent of
hydrated phase formation and their decom-
positions at higher temperatures. But MgO
addition was found to enhance the strength
considerably due to faster bond formation at
low temperature and liquid phase formation,
as observed in the micro-structural study, at
high temperatures. |
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Figure 4 FESEM photomicrographs of the 1600 °C sintered castables,

(A) q = 0.21 without MgO, (B) q = 0.21 with 1 % MgO, (C) q = 0.29 without MgO and (D) q = 0.29 with 1 % MgO (©R. Sarkar)

48 Refractories Manual 2018 www.interceram-review.info


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The authors thankfully acknowledge the
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1 Department of Ceramic Engineering, National
Institute of Technology, Rourkela, Odisha, (India)

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67th Volume 2018 Refractories Manual 49