R E SE A R CH A N D D E V ELO PM EN T | B i nders

Binders for Refractory Castables:

An Overview
R. Sarkar1
Abstract: A binder for refractory castables is a bonding material that bonds a loose powdery mix,
retains its shape after casting and allows the cast shape to set and harden for handling and further
processing. A binder also improves sintering, as the castables are not compacted during shaping,
causing poor densification and strength. Initially, plastic clay was used as a binder for castables, but
soon it was found to have more disadvantages than benefits. Next came the alumina cements with
an alumina content below 50 %, but this resulted in degraded hot properties due to low
temperature liquid phase formation. The performance of the castables was improved with an
increase in the alumina content of the cement. However, the presence of lime continued to be a
concern with high temperature uses. Then came the binders without lime, like sol-gel, hydrated
alumina, phosphates, etc. Different bonding systems have their own advantages and limitations and
are being used as per the requirements of the application site. The present paper reviews the
different types of binders available for castables and gives an elaborate idea for their functioning
and performance.

Keywords: castable, binder, alumina cement, colloidal system, hydratable alumina, chemical binder

1. Introduction
Unshaped refractories, especially castables,
are replacing conventionally shaped refrac-
tories in most application areas in the user
industries due to various advantages, like the
ease of production and easy installation
technique, no firing, fewer joints resulting in
lower corrosion, etc. [1]. The advantages have
inspired refractory scientists and manufac-
turers to continuously investigate these
materials in depth and to improve their qual-
ity and performance. Since the early 1960s,
the commercial availability of pure calcium
aluminate cements (CACs) with higher alu-
mina content has made castables purer and
has made them applicable for various
high-temperature applications [2].
Refractory castables are a blended mix-
ture of different fractions of refractory aggre-
gates and fines with bonding agents and
additives. They are supplied by manufactur-
ers as loose dry powders, mixed with a liquid
(usually water). In the user industry, they are
cast or poured into the application area to get
the desired shape and dimensions, become
rigid by hydraulic or chemical setting and are
then fired for densification and strength
development [3]. The proportions of each of
the components used in the castable compo-
sition are varied to achieve the desired prop-
erties and to suit the intended application.
The bonding agents or binders are a must in
a castable composition, as they contribute to
the development of strength both at ambient
and elevated temperatures. Binders also help
to retain the shape at green conditions, as no
compaction is involved during the shaping
process of the castables [4]. Binders also con-
tribute to the sintering of the castable com-
positions. The mass transfer in the castable
for sintering is less during firing, as the dif-
fusion path is much higher because no com-
paction is involved during shaping, which
would then result in poor densification and
strength [4]. Binders provide finer particles,
causing enhancement of sintering and
strength. In earlier days, about a century ago,
plastic clay was used as a binder for unshaped
refractories. The plastic nature of the clay
mass helped to retain the shape, the sticki-
ness provided the strength at low tempera-
tures and finer sized particles improved the
sintering. However, drawbacks like the
higher water requirement, huge shrinkage,
weak strength development both at ambient
and elevated temperatures and poor hot
properties were also associated with clay
binders.
Plastic clay binders were immediately
replaced by alumina containing cements,
once the latter was developed and commer-
cially available. Initially, the alumina content
of cement was lower, which resulted in infe-
rior high-temperature properties. Gradually
with time, the alumina content in cement
was improved, and the quality and proper-
ties of the castable along with its alumina
content also improved significantly. How-
ever, the demand for higher-temperature
applications from the user industries also
increased continuously. The presence of lime
in the cement composition resulted in poor
hot properties due to low melting phase for-
mation. Thus, the trend of reducing the CaO
content in the composition of castables,
either by reducing the cement content or by
reducing the amount of CaO in the cement,
came into practice with the addition of dif-

44 Refractories Manual 2020www.interceram-review.info

Author
PROFESSOR RITWIK
SARKAR
(ritwiksarkar@rediffmail.
com), NIT, Rourkela, India,
has about 15 years of expe-
rience in Ceramics and Re-
fractories. He worked with
IFGL Bioceramics Ltd., IF-
GL Refractories Ltd, CG &
CRI, R&D of ACC Ltd., and
H&R Johnson Ltd., all in In-
dia, and at the IKKM, RWTH
Aachen, Germany (DAAD
Fellowship). He has re-
ceived many awards in his
career for academic ex-
cellence and his contribu-
tions to Ceramics and Ma-
terials Science, including
the Young Scientist Award.
A life member of the Indi-
an Ceramic Society & Indi-
an Institute of Ceramics, Dr.
Sarkar has more than a 100
research publications and
9 patents to his credit.
ferent property-modifying additives. Still the
presence of lime cannot be avoided, and
there are limitations to the application tem-
perature. Refractory researchers, manufac-
turers and users worked continuously to find
a replacement for cement binders and finally
came up with different cement-free bonding
systems, like sol-gel, hydrated alumina,
phosphates, etc. However, all the different
bonding systems have their own limitations
and are practically used with certain condi-
tions and constraints. Moreover, commercial
high-alumina cement is still used today as
the major bonding material for castables.
2. Alumina cement
In the early days of the nineteenth century,
when the concept of unshaped refractories
was just emerging, people planned to use
69th Volume 
ordinary Portland cement (OPC) as a binder
due to the similarity of the castable with con-
cretes. However, OPC contains about 60 to
65 % CaO, which is highly hygroscopic and
basic in character, and complete dehydration
of the hydrated bonds resulted in collapse of
the structure above ~625 °C and even at
400 °C under thermal cyclic conditions [3].
Hence, the use of OPC in unshaped refracto-
ries was a failure from the beginning.
The first patent for alumina-based
cement was obtained by Lafarge in 1908 in
France, and the commercial production of
alumina-based cement was also established
by Lafarge in 1913. However, these alumina
cements were developed for the construction
industry due to their better corrosion resist-
ance and u nder-water applications.
High-temperature applications of alumi-
na-based cements were started in the mid
1920s, both in the US and in France [5]. Ini-
tially, calcined clay and crushed fireclay
bricks were mixed with bauxite-based alu-
mina cement for refractory applications.
However, these materials were of very low
grade due to the poor mixing and applica-
tion technique and were used only for
low-temperature applications.
In the initial days, the alumina content
in cement was low, the quality of alumina
cements was inferior and the technology
was not fully developed. To obtain a good
cold strength in castables, a higher amount
of cement was previously used in the range
of 15–20 mass-%. Hence, the water require-
ment for cement hydration was also very
high, about 12–20 mass-%. These castables,
termed conventional cement castables
(CCC), lose their unbound (physical) mois-
ture during drying and chemically (hydrau-
lic) bonded moisture during firing, which
results in a porous and weak refractory
structure [6]. So, high density and strength
were difficult to attain. Also the high
amount of lime in cement easily reacts with
the alumina and alumino silicates fines and
forms liquid phases at a much lower tem-
perature. Low-melting compounds like
anorthite (CaO∙Al 2O3∙2SiO2 or CAS2) and
gehlenite (2CaO∙Al 2O3∙SiO2 or C2AS) were
present at the application temperatures in
these castables and restrained their ther-
mo-mechanical performance and chemical
resistance. Hence, these castables were only
applicable for low temperatures.
With time, the application temperature
in the refractory user industry, particularly
the metallurgical industry, increased consid-
erably to produce purer and better quality
products. This in turn led to a demand for
higher application temperatures for the
castables. Again, as the CaO content in the
composition of castables is the main limiting
factor for high-temperature applications, the
amount of CaO should necessarily be
reduced. The primary source of CaO in
refractory castables is cement, and so to
improve the performance of castable refrac-
tories, technology needs to enable the reduc-
tion of the content of CaO or cement in the
composition [7].
Numerous research projects began with
the aim of reducing the cement content in
castables. The first introduction of the low
cement castable (LCC) composition was pro-
posed by Prost and others [8], wherein the
cement wa s d ra st ic a l ly reduced to
4–6 mass-% with a near equal amount of
water. This reduction in the cement content
without compromising the properties was
possible by the use of flow modifying addi-
tives, namely silica fume and dispersants.
Fine particles of silica fume improve the
packing due to better filling of finer voids
and also the f low behaviour due to their
spherical shape. This development of the
reduction of cement from 12–18 % to 4–6 %
increased the application temperature from
a range of 1300–1350 °C to 1500–1550 °C.
This has encouraged refractory scientists
and engineers to further reduce the cement
content and finally develop ultra-low cement
castables (ULCC) [9, 10], which was possible
by controlling the aggregates and their gran-
ulometry (particle size distribution), the
quality of the cements, the use of additives
and micro-fine powders.
Also, refractory scientists were in search
of cements with a low CaO content, without
compromising much on the bonding char-
acteristics. The research work on reducing
the CaO content of alumina cement has also
positively inf luenced the development of
castable industries for high-temperature
applications. About half a century ago, alu-
mina cement used to contain Al 2O3 in the
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Table 1 Details of different types of commercially available alumina cements (© Sarkar)

Average alumina
40 50 65 70 75 80
­content [%]
Refractoriness or PCE
1270−1290 1430−1450 1460−1520 1590−1620 1650−1680 1770−1810
[°C]
Al2O3 37.5−41.5 50.8−54.2 64.1−65,9 68.7−70.5 73.1–75.5 79.5−82.0
CaO 36.5−39.5 35.9−38.9 32.5–34.1 28.5−30.5 23.2–24.5 16.2−17.8
SiO2 2.5−5.0 4.0−5.5 0.3–1.0 0.2−0.6 0.3–0.8 0.35
Fe2O3 14.0−18.0 1.0−2.2 0.6–1.2 0.1−0.3 0.1−0.3 0.2
TiO2 < 4.0 < 4.0 < 1.0 < 0.4 < 0.4 < 0.3
MgO < 1.5 < 1.0 < 1.0 < 0.5 < 0.5 < 0.5
Na2O + K 2O 0.4 < 0.5 < 0.5 < 0.5 < 0.6 < 0.7
Major phase CA CA CA CA, CA 2 CA, CA 2 CA 2 , CA, Aα
C12 A 7, C 2 S, C 2 AS,
Minor phase C12 A 7, C 2 AS, C T C12 A 7, C 2 AS C12 A 7, Aα C12 A 7, Aα C12 A 7
C4AF
Blaine surface area
2850−3450 3750−4250 3800−4200 3800−4400 4000−6000 8000−12000
[cm2/g]
Average size, d50 [µm]
18 14 12 12 10 6
(Laser)
CA = calcium aluminate; CA 2 = Calcium di-aluminate and Aα = alpha alumina (corundum)

range of 35–40 mass-% and CaO between
50–55 mass-%, which was technologically
upgraded to today’s high-alumina cements
containing alumina up to 80 % with CaO
around 17–18 %.
Presently, alumina cement is classified
into different grades as per the alumina con-
tent. All these grades have different raw
materials, processing conditions, properties
and application areas. Low-alumina contain-
ing cements, developed in the early days, are
still in use and are manufactured from the
natural raw materials limestone and bauxite.
Impurities associated with the raw materials
are present in the cement composition. They
adversely affect its properties and restrict the
application above 1250 to 1300 °C. A purer
variety of natural raw materials can only
improve the properties slightly, and also the
application temperatures. High pure alu-
mina cements are prepared mostly from syn-
thetic raw materials, like hydrated lime (pro-
duced by hydration of calcined limestone)
and calcined alumina (from Bayer’s process).
These high pure cements, generally termed
high-alumina cement (HAC), also have very
high alumina content, even up to 80 mass-%
Al2O3, and can be used up to temperatures of
1700 °C. The improvement in the quality of
the cement is possible with the use of
high-purity processed or synthetic raw mate-
rials replacing natural ones, improved pro-
cessing conditions, finer milling, etc. The
details of the different types of alumina
cements that are commercially available and
being used by the castable industry are pro-
vided in Table 1 [11–14].
Calcium aluminate cement is based on
the CaO–Al2O3 phase diagram, as shown in
Figure 1 [3], and the different phases that
form in the system are also mentioned. Cal-
cium mono-aluminate (CaO∙Al 2O3, CA) is
the principal reactive desirable compound
that hydrates and provides the hydrated
bond in the castable. Calcium di-aluminate
(CaO∙2Al2O3, CA2) is the secondary hydrau-
lic phase, which is less hydraulic than CA.
There may also occur some unwanted
phases, like dodeca-calcium hepta-alumi-
nate (12CaO∙7Al2O3, C12A7), which is a meta-
stable phase and has a flash setting character,
calcium hexa-aluminate (CaO∙ 6Al2O3, CA6),
which is non-hydraulic in nature, and other
minor phases based on the impurities pres-
ent, like gehlenite (2CaO∙Al 2O3∙SiO2), cal-
cium titanate (CaO∙TiO2), calcium ferrite
(CaO∙Fe2O3), tetra calcium alumino ferrite
(4CaO∙Al 2 O3 ∙ Fe 2 O3), etc. Mostly, these
phases are also non-hydraulic in nature. The
presence of 3CaO∙Al2O3 and 12CaO∙7Al2O3
phases (this may occur with a high lime con-
tent) makes the cement very fast setting, or
f lash setting, due to the high presence of
lime. Table 2 shows a detailed hydration
scheme of the two main phases of calcium
aluminate cements [3].
Both physical and chemical changes take
place when water is added to the cement.
The hydration converts the anhydrous
cement powder into various hydrate phases
[15–18]. This whole process can be divided
into three stages, namely dissolution, hydra-
tion and precipitation. Hydration is initiated
by the hydroxylation of the cement surface
followed by dissolution of the anhydrous
cement particles in water, which liberates
calcium and aluminium ions [19]. The dis-
solution continues with a continuous
increase of Ca and Al ion concentrations
until their saturation limit is reached. The
initial dissolution is followed by an induc-
tion period during which hydrate nuclei
attain a critical size and quantity. After this,
precipitation of hydrate phases occurs with
a consequent increase in the mechanical
properties [20]. The dissolution period can
be associated with the working time and

46 Refractories Manual 2020www.interceram-review.info

massive hydrate precipitation with the hard-
ening and mechanical properties acquisi-
tion time [21]. The driving force of the
hydration reactions is the lower solubility of
the hydrates compared to the anhydrous
species. The ambient temperature signifi-
cantly modifies the hydration behaviour as
the solubility of anhydrous phases changes
with temperature [22].
Water that is added in the castable com-
position during mixing has two major roles:
Temperature [°C]
it is required for the complete hydration of
the cement particles and it also allows the
composition to flow. Hence, the amount of
water used during mixing plays an impor-
tant role in the development of various prop-
erties. A lesser amount of water will not allow
the cement to hydrate completely, which
causes poor strength development and also
results in poor flow characteristics. Again,
any excess water will cause a porous struc-
ture after drying and will result in reduced
density and strength. Also, excess water may
enhance the gravity separation in the com-
position and may increase the growth of the
cement hydrates, causing larger hydrate crys-
tals and poor strength [15].
When alumina cement is used in a refrac-
tory castable and at the same is mixed with
water at the application site, hydrated phases
are formed, and they provide strength at low
temperatures. The two major hydrated
phases, namely CAH10 and C2AH8, are met-
astable in nature and convert to stable
C3AH6 phase during curing and drying. All
the CAH10 and C 2AH8 phases completely
convert to C3AH6 phase below 200 °C, and
during firing above 300 °C this C3AH6 phase
gets dehydrated to form a metastable C12A7
phase.
Decomposition of the hydrated phases
during heating disrupts the bonds of the cast
product in the cement-bonded castable, and
the strength falls drastically. This generally
happens above 300 °C. The degradation in
strength is stronger when the amount of
cement in the composition is higher. The loss
in strength is associated with the drastic
increase in porosity due to dehydration [23–
25]. It has been calculated that 1 cm 3 of
CAH10 converts to 0.489 cm3 of solid hydrate
phases and 0.568 cm3 of water [24]. Removal
of this moisture causes void space account-
69th Volume 
2000
1800
1600
1540
1400
C3 A
0 20
CaO
Figure 1 CaO–Al2O3 phase diagram [3] (© Sarkar)
ing for more than the remaining hydrated
phase volume. If the conversion takes place
sufficiently slowly, the porosity that develops
because of this change in volume may be
filled with newly formed hydration products
from this secondary hydration [15]. Strength
development again starts with the initiation
of sintering in the castable composition, gen-
erally above 1000 °C.
When the cement-containing castable is
heated above 300 °C, the C12A7 phase starts
reacting with the finer alumina particles
present in the matrix and forms a CA phase,
which occurs above 900 to 1000 °C. At even
higher temperatures the CA phase formed
reacts with the fine alumina present and
forms CA 2 (grossite) phase. Hence, for high
pure alumina-based castables, the final
phases in the fired body will be corundum
and grossite, as is shown in Figure 2 [26].
During the firing, fine particles generated by
2054
Liquid Phase
1830
1765
1754
1604
1597
CA2
CA6
CA
1362
40 60 80 100
mass-% Al2O3 Al2O3
the decomposition of cement hydrates help
in sintering of the castable, which starts
above 900–1000 °C. Hence, the strength of
the castable again increases above this
temperature.
Cements containing very high amounts
of alumina (~ 80 %) contain CA 2 as the pre-
dominant phase. Hence, these cements may
have reduced hydraulic activity due to a lower
lime content. To enhance the hydraulic activ-
ity, these cements are processed [27] for
increased fineness by longer milling,
increased reactivity of CA2 phase by restrict-
ing grain growth, etc. These cements are ben-
eficial, as the CA 2 phase will result in excess
AH3 formation during hydration, thus filling
the pores of the castable composition better
and resulting in improved compaction and
strength values. Also, the CA2 phase has a liq-
uidus temperature about 160 °C higher com-
pared to that of the CA phase (Figure 1), and
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Table 2 Detailed hydration scheme of the two main phases of calcium aluminate cement [3] (© Sarkar)
Temperature range Reactions of cement phases
For CA For CA 2
Below 18 °C (or 20 °C) CA + 10 H = CAH10 CA 2 + 13H = CAH10 + AH 3
Between 18 °C (or 20 °C) to 30 °C (or 35 °C) 2CA + 11 H = C 2 AH 8 + AH 3 2CA 2 + 17H = C 2 AH 8 + 3AH 3
Above 30 °C (or 35 °C) 3CA + 12H = C 3AH 6 + 2AH 3 3CA 2 + 21H = C 3AH 6 + 5AH 3
O n ageing /curing (with increasing time and 2CAH10 = C 2 AH 8 + AH 3 + 9H
temperature and depends on humidity) 3C 2 AH 8 = 2C 3AH 6 + AH 3 + 9H

is thus better suited for high-temperature produces a liquid phase by reacting with sil-
applications. ica and other impurities available in the sys-
tem and deteriorates the hot properties. For
high cement-containing compositions, CaO
3. Colloidal (sol) systems forms low-melting compounds in the CaO-
The use of calcium aluminate cements Al 2O3-Fe2O3, CaO-Al 2O3-SiO2 systems, etc.
restricts the high-temperature applications Reduction in the cement content reduces the
of castables, as the lime present in the cement amount of CaO in the castable system, and
Anupam 6C1
2000 Alumina
Grossite
Counts
thus reduces the amount of liquid phase and
results in reduced degradation of the hot
properties [2, 4, 15, 28, 29]. However, this
reduction demands other fine materials,
mainly acting as fillers, like fume silica.
Again, this is also associated with increased
liquid formation in the CaO-Al2O3-SiO2 sys-
tem. Hence, improvement in hot properties
is marginal. Also, the interactions among the
cement particles, fine filler materials and the
property modifying additives make the
whole castable system intrinsically more sen-
sitive [30]. Again, as CaO determines the
basic character of the composition, the cor-

rosion resistance of cement-containing sys-

tems is not the best. Drying and firing of
cement-containing castables also requires
1000 special attention, as the removal of moisture
may cause explosion, spalling and cracking.
Due to the limitations of cement-bonded
castables, refractory scientists worked to
develop cement/CaO-free binder. Among
the different possibilities that were success-
ful, also commercially, colloidal silica/silica
sol is the most important one. Besides its
Peak List high stability and higher solid content, the
Anupam 6C1
factor that favours silica sol is the possibility
of mullite formation in the alumina-based
compositions [31–33].
00-011-0661 Silica sol is an aqueous colloidal dispersion
Alumina
of nano-sized and spherical-shaped silica par-
ticles [33–35]. The sol particles are so small
that they suspend in water, and gravitational
00-046-1475 force cannot settle them. Again they are large
Grossite enough that they do not pass through a mem-
brane, allow other molecules and ions to pass
through them freely, and they do not enter
20 30 40 50 60 70 into the intermolecular spaces of water (get
2θ [°] dissolved). Colloidal silica is a clear liquid that
Figure 2 Phase analysis of fired alumina cement containing high alumina castable [26] (© Sarkar) is heavier than water due to the presence of

48 Refractories Manual 2020www.interceram-review.info

suspended silica particles and is electrostati-
cally stabilized to form a stable suspension.
[SiO4]4- tetrahedra, the basic units of colloidal
silica, are randomly distributed in water and
hence produce an amorphous character [3].
For the manufacturing of silica sol, an alka-
li-silicate (sodium silicate) solution is neutral-
ized to form silica nuclei, which are only a few
nanometres in size.
Polymerization of these nuclei occurs
when the sol is unstabilized by changing the
pH-value of the suspension, temperature, etc.
These affect the stability of the individual sol
particle’s nuclei; they agglomerate and grow
in size. Colloidal silica is stable in the pH
range of n 8–10, but if the pH value exceeds
10.5, it is precipitated or coagulated [36]. So
to retain the sol in a stable condition, it must
remain undisturbed, especially without any
change in pH and temperature. A consider-
able change in the temperature from the sta-
bility temperature range will destabilize the
sol, resulting in coagulation of particles and
settling. Other than the refractory applica-
tions, colloidal silica is also important for the
manufacture of coatings catalysts and mois-
ture absorbents, in the paper industry, etc.
Application of silica sol as a binder replac-
ing alumina cement is a great upliftment for
castable technology, as it allows the making
of castables without cement, avoids all the
limitations of cement-bonded castables and
results in improved properties [37–38]. The
individual sol particles are very fine in size
and spherical in shape, and thus, they
improve the flow behaviour of the castable.
Again, strength development in a sol bonded
composition occurs through the formation
of a ‘gel’ structure, by linking individual sol
particles together to form a branched chain,
in a process called ‘gelation’ [39]. This gel
structure surrounds the castable particles
and encapsulates them through a three-di-
mensional skeleton network formation,
which provides suitable mechanical strength
after drying. [2, 15, 39–44]. This network
structure provides strength to the castable at
low temperatures. On heating, removal of
moisture occurs, and the hydroxyl groups
(Si–OH) of sol convert to siloxane bonds
(Si–O–Si), and thus results in a rigid
three-dimensional network [34, 44]. Addi-
tives (called gelling agents) also help to
69th Volume 
Counts
1600 AKASHCS6,RD
900
400
100
0
20 30
Figure 3 Phase analysis of fired silica sol containing high alumina castable [49] (© Sarkar)
remove H from the SiOH groups and help in
the gelation process by destabilization of the
sol. CaO, or cement, MgO favour the anionic
reaction by the formation of respective
hydroxides, Ca(OH)2 or Mg(OH)2, and with-
drawal of H ions from the Si–OH and pro-
mote Si–O–Si formation, thus enhancing the
gelation rate [45–46].
The release of water from silica sol-
bonded castables occurs at a lower temper-
ature than complete dehydration of calcium
aluminate-bonded systems, so a better
dense product is obtained after drying [47].
Again, as the moisture is released from the
gelled structure when drying, a porous and
highly permeable structure is formed [44].
Thus, the drying and total processing time
is reduced, which also decreases the risks of
cracking and explosive spalling. However,
this porous structure may decrease the
mechanical strength and affect the creep
rate [44]. Again, fine silica particles from the
sol present in the castable matrix react with
the alumina fines available and form mullite
at a lower temperature. This improves the
hot properties and corrosion resistance and
also increases the thermal shock resistance
of the castable [48]. Silica sol-bonded alu-
mina castables contain corundum as the
major phase, with mullite as the minor
phase, after firing, as shown in Figure 3 [49].
Fine gel particles make for better sintering
of the castable, result in ceramic bond for-
mation at a lower temperature [43, 44,
Alumina
Mullite
40 50 60
2θ [°]
50–53], and produce better properties com-
pared to cement-bonded ones [37, 38, 54].
The advantages of colloidal/sol bonding
over cement bonding are listed below [3].
}} Less mixing time due to the absence of
additives (like deflocculants, anti-set-
ting agents, etc.)
}} Nano-sized spherical particles improve
the flowability even with lower water
content.
}} The higher viscosity (than water) helps
with the separation of the refractory
particles and, thus, improves flowability.
}} Drying time and drying defects are re-
duced due to the lowering of free wa-
ter for mixing and the permeable gelled
structure.
}} Early formation of mullite in alumi-
na-based compositions improves corro-
sion resistance and hot strength.
}} Better high-temperature properties
due to the absence of low-melting com-
pounds in CaO-Al2O3-Fe2O3 and CaO-
Al2O3-SiO2 systems
}} Better high-temperature properties re-
sult in a longer campaign life and re-
duced downtime.
}} Longer shelf-life due to the absence of
any hygroscopic phases
}} Fine colloidal particles from the sol coat
the non-oxides more effectively, result-
ing in an improved oxidation resistance
and better performance for non-oxide
containing compositions.
2020 Refractories Manual 49
R E SE A R CH A N D D E V ELO PM EN T | B i nders
Table 3 Details of different colloidal (sol) binders [63] (© Sarkar)
Particle size range [nm]
Solid content (Ignition basis at 1000 °C)
Phase analysis at 1200 °C
Hot strength of castable at 1400 °C [MPa]
Blast furnace slag penetration in castable [mm ]2
However, not all of these are good for silica
sols. The presence of unreacted silica in the
fired castable produces liquid phase at a
lower temperature due to the large surface
area (surface energy). This results in
degraded high-temperature properties, par-
ticularly in an alkali environment, thus caus-
ing limitations in high-temperature applica-
tions [31–33, 44, 55]. This has encouraged
refractory researchers to look for other sol
systems that are devoid of such disadvan-
tages. Among the other sol bonding systems,
mainly alumina, mullite, magnesia and spi-
nel sols are tested for refractory castables.
But there is not enough literature available
on such studies. The major hindrances for
such applications are various processing dif-
ficulties, such as a lower solid content of sol
leading to poor bonding activity, weak sta-
bility of sol, a high water demand for process-
ing, etc. [31, 32, 44, 55]. Also, in most of these
trials, the colloidal binder was used as a sup-
portive bond along with alumina cement,
causing difficulty in identifying the advan-
tages of any individual bonding system and
brought about disadvantages of the cement
bond in the castable system [52, 56–57].
Studies are also available on the use of
other sol systems as the sole binder in
high-alumina castable compositions, like
alumina sol, boehmite sol, mullite sol, spinel
sol, etc. [58–62]. High-quality castable prop-
erties have been reported, especially for the
high-temperature properties, like hot
strength, corrosion resistance, thermal shock
resistance, etc., in comparison to silica sol
and cement-bonded compositions, but with
reduced dried strength. The absence of any
impurity and low-melting phase in the com-
positions were the reason for the better prop-
erties. Also, these studies indicated that
50 Refractories Manual 2020www.interceram-review.info
Alumina sol Mullite sol
10– 60 10–100
6 12.5
α-Alumina Mullite
12.2 15.0
530 500
batch compositions containing a greater
number of finer fractions in the matrix show
better properties. Some property details of
these sol systems are provided in Table 3 [63],
along with that of commercial silica sol.
4. Hydratable alumina
Hydratable alumina (HA) binders are being
increasingly used in zero cement castables
and have attracted great attention for their
unique character of providing alumina as the
remnant product after firing [64–66]. They
do not introduce any secondary phase or
component and so high purity of the system
can be maintained, and a castable of more
than 99 % purity is feasible. In this bonding,
the matrix phase contains the binder in the
form of aluminium hydroxide gel and coats
the grains of a castable by a non-reactive pro-
tective alumina layer. Thus, a castable com-
position with both the aggregate and matrix
phases as alumina is possible, which results
in improved slag resistance, fracture tough-
ness, hot strength, and resistance against
thermal shock and impact, etc. The absence
of lime and other impurities also cancels the
chances of the formation of any liquid phase,
and high strength develops due to the
ceramic bond formation at high tempera-
tures. The development of such a castable
only consisting of alumina was first reported
in Japan [65]. Hydratable alumina binders
are especially useful in developing stable
bonds for high-purity metallurgical pro-
cesses where the uptake of Ca and Si is a
major concern.
Hydratable alumina is a low crystalline
mesophase transition alumina (e.g. θ, ρ),
which similarly to cement hardens on reaction
with water [67]. It is manufactured from gibb-
Spinel sol Silica sol
10–200 10–80
8 31.5
Tridymite & silica
Spinel
glass
16.5 8.0
360 610
site in two major ways: a) vacuum calcination
(~ 550 to 600 °C) and b) flash calcination
(between 600 to 900 °C) [65, 67–69]. The
resulting product is a highly reactive tiny tran-
sition alumina, also called ρ-alumina. Because
it is very reactive in nature, this alumina has
the tendency to rehydrate in the presence of
moisture, which is why it is called hydratable
alumina. This hydration provides the bond-
ing character in refractory castables. The
hydration reaction is as follows in (1).
ρ-Al 2O3 + H2O → Al 2O3∙3H 2O (Bayerite)+
Al2O3∙(1–2) H2O (Boehmite gel)(1)
This hydration reaction is markedly depend-
ent on the curing temperature; precisely it is
very slow at 5 °C but quick at 30 °C. It also
depends on the water ratio; the formation of
bayerite tends to be lower at lower water con-
tents. Additives also control the formation of
the hydrate phases; the addition of alkali
metal salt enhances the formation of bayerite
phase, whereas organic carboxylic acid
enhances the formation of boehmite gel
phase [65].
The hydration reaction forms a thick
layer of gel, which subsequently crystallizes
partly to bayerite and boehmite phases, and
the remaining portion as amorphous gel.
This gel formation is dependent on the
hydration temperature and the pH-value of
the system. The bayerite crystals form an
interlocking structure and fill the pores and
the interfacial defects along with the formed
gel. They also form a honeycomb structure
on the refractory aggregates and develop
green strength. The formation of crystals
also occurs on the surface of the aggregates,
and the crystals link with one another, con-
necting adjacent grains in the surrounding
matrix. During heating, all the hydrated
phases lose their chemically bonded water
and convert to stable α-Al2O3 fine particles.
These tiny alumina particles help in sinter-
ing at higher temperatures to develop
ceramic bonds faster and enhance the
strength [1, 67].
HA-bonded castables also have some
major drawbacks. They have a longer mix-
ing time compared to cements because of
the high specific surface area (~ 200 m 2/g)
[43, 44, 66, 68]. Users have a tendency to add
excess water to attain faster mixing and
f low consistency. This again extends the
working time and affects density, strength,
and corrosion resistance. Strength develop-
ment in these castables depends on the sur-
face hydration of hydratable alumina parti-
cles. If the mixing and curing temperature
of the castable is very low (< 18 °C), the
hydration tendency is also low, resulting in
poor strength development. Hence, in
colder places the addition of hot water and/
or localized heating facilities during mix-
ing and curing are required for proper
hydration and strength development.
Again, in a hot mixing and curing environ-
ment (> 38 °C), the chances of localized and
flash setting is high, which causes non-uni-
form and poor strength in the castable. So
the mixing, casting and curing temperature
is important.
Also the structure formed after the HA is
consolidated causes a significant decrease in
the porosity and permeability level of the
castable, which increases the chances of
explosive spalling during drying [1, 64]. The
use of organic (bake-out) fibres that melt or
shrink at temperatures below 150 °C is
essential to allow passage for moisture
removal, vent the matrix and to add protec-
tion from spalling at critical temperatures.
For optimum strength development and to
avoid cracking or explosive spalling, proper
precaution is essential for the dewatering
process. Moreover, there is a decrease in the
mechanical strength during firing in the
range 300–1000 °C, which is associated with
the formation of a porous structure due to
the decomposition of the hydrates [65]. The
use of hydratable alumina as the bonding
material in castables is also economically
unfavourable.
69th Volume 
5. Chemical bonding and
phosphates
Chemical bonding refers to a group of mate-
rials that are non-hydraulic and inorganic in
nature. They form bonds through chemical
reactions within themselves or with the
castable components with time, temperature
or in the presence of additives. In order to
maximize the operational time for the user
industries, especially in petrochemical appli-
cations, chemically-bonded castables, par-
ticularly phosphate-bonded ones, are impor-
tant because of their short setting time (com-
pared to other hydraulic binders) and inter-
esting properties, such as the high green
strength, good adhesion, reduced chances of
cracking under high heating rates after cur-
ing, etc. [69, 71, 72].
Chemical bonding started with silicates
long ago [73], especially sodium silicate,
which still finds suitability in low-temper-
ature applications. The formation of
low-melting compounds due to the pres-
ence of sodium ions does not allow the
application of these silicate-bonded materi-
als in high-temperature environments and
is important for investment casting. Com-
mercial silicate binders are available in
loose powder form or in liquid solution
form and chemically as Na 2O∙ x SiO2∙ yH2O,
wherein the value of x lies between 1 to 4.
However, for refractories an x value between
2 to 3.35 is commonly used [76]. A typical
chemical composition of the sodium sili-
cate binder is Na 2O between 7–13 %, SiO2
between 25–33 % and H 2 O between
59–68  %. Setting and hardening of this
bonding occurs by drying or heat treatment
and is often time consuming. Sodium sili-
cate (also called water glass) is an air-setting
binder that works at room temperature. The
setting mechanism is a gelification process
in acidic conditions [29]. To improve this
setting/hardening character, a gelling agent,
like metal powder or alkaline metal silicate,
and a hardening agent, like aluminium
phosphate [75], is added.
Among the different chemical bonding
types available for castables, phosphates are
the most vividly studied and widely used
material. Details of phosphate bonding and
its suitability for refractories have been
known from the detailed studies of Kingery
since the 1950s [76–79], but its commercial
exploitation and industrial use took longer.
Phosphate bonding is primarily important
for ‘plastic’ refractories. As it contains no
lime-bearing or hydratable compound, it
does not set easily at ambient conditions. It is
free from atmospheric setting. That means it
remains moistened for an indefinite time,
and it also remains workable, behaving like a
plastic mass [70]. This gives an extensive
working time for repair mass. Phosphate
bonding is mainly important for its good
adhesion, especially with metallic parts, and
because it has a lesser chance of cracking
during heating, allowing faster installation
and less downtime [70, 80, 81]. However,
phosphate bonding is used in limited areas
due to its poor strength development at low
temperatures. A weak and porous structure
develops in phosphate-bonded castables due
to the use of a relatively high amount of liq-
uid during installation, which results in poor
strength, low corrosion resistance and easy
wear of the lining. Also due to its acidic char-
acter, phosphate bonding does not work well
in basic environments. The bond can be
developed within the castable by the reaction
between ortho-phosphoric acid (H3PO4) and
alumina or by addition of mono-aluminium
phosphate [MAP or Al(H2PO4)3] [70]. This
bonding is not used for silica or magne-
sia-based compositions. Silica does not react
with phosphoric acid at low temperatures
and also forms low-melting compounds
SiO2∙ P2O5 and 2SiO2∙ P2O5, causing deforma-
tion of the refractory between 1100–1300 °C.
Again, magnesia reacts with phosphoric acid
instantly and sets in a flash. Also, the differ-
ent MgO–P2O5 compounds formed in the
composition are low melting: they all melt
below 1327 °C.
Phosphoric acid (H3PO4) solution does
not react with alumina at low temperatures,
and so the castable does not set. It only reacts
when the composition is heated between 127
to 427 °C to form mono-aluminium phos-
phate (MAP) Al(H 2PO 4)3. This reaction
starts at room temperature with Al(OH)3,
and so for faster setting initiation, hydrox-
ides are also included in the alumina-based
castable compositions. This formed MAP
decomposes to form ortho aluminium phos-
phate (OAP) above 732 °C, and this decom-
2020 Refractories Manual 51
R E SE A R CH A N D D E V ELO PM EN T | B i nders
position may continue until 1327 °C. A fur-
ther increase in temperature decomposes
the phosphates to pure alumina and phos-
phorus pentoxide (gas) above 1350 °C. The
details of the reactions (2) to (5) are shown
below [70, 72, 82],
6H 3PO 4 + Al 2O3 = 2Al(H 2PO 4)3 + 3H 2O
(temperature 127−427 °C)(2)
3H3PO 4 + Al(OH)3 = Al(H 2PO 4)3 + 3H 2O
(room temperature)(3)
Al(H 2 PO 4) 3 = AlPO 4 + 3H 2 O + P 2 O 5
(temperature 732−1327 °C)(4)
2AlPO4 = Al2O3 + P2O5 (above 1350 °C)(5)
Hence, after firing there is no remnant phos-
phorus phase in the composition of the casta-
ble, and the composition becomes pure alu-
mina. So there is no effect of any secondary
phase in the castable from its binder, as in the
case of cement and silica sol-bonded ones, and
the original castable composition can have its
own properties. However, the purity of the
composition alone does not dictate the perfor-
mance of a castable, and phosphate bonding
is associated with a few drawbacks. The casta-
bles are very weak, and strength development
is very slow in ambient conditions. To improve
the quality, setting additives are added,
namely MgO, CaO, calcium aluminates, etc.
[83]. These basic materials react instantly with
the acid/acidic component of the bond and
result in the formation of amorphous/crystal-
line phosphates, causing hardening, setting
and development of strength [70, 84] .
Also, for proper f low consistency and
workability a good amount of free water is
required, which necessitates a slow and long
drying schedule. During firing, moisture
and P2O5 gas are released due to decompo-
sition of different phosphates compounds,
causing porosity in the castable lining. The
porosity generated at high temperatures is
difficult to remove, and finally a porous and
weak sintered product is developed, which
has low strength and is vulnerable to corro-
sion, abrasion, impact and t herma l
fluctuations.
Again, when MAP is added as a water-sol-
uble condition, a relatively high bonding
strength and a reaction with basic and
amphoteric raw materials at low tempera-
tures is obtained [75, 84, 85]. This produces
reasonably quick setting and moderate green
52 Refractories Manual 2020www.interceram-review.info
strengths. However, improper mixing and
poor dissolution of phosphate may result in
inconsistent bonding and poor properties of
the castables. The bonding characteristics
depend on the size of the phosphate powders,
dissolution of phosphates in water and reac-
tion and mixing processes with the refrac-
tory particles in the composition. Careful
drying and heating are also necessary to
remove the moisture completely and to avoid
cracking and spalling.
6. Conclusions
For castables, binders are essential for the
retention of shape at green conditions and
strength development at ambient and elevated
temperatures. Binders also help to sinter the
castables by providing nascent fine particles,
so that the compaction process does not result
in castables with poor densification and
strength. Alumina cement and hydratable
alumina binders work on the principle of
hydration, but the decomposition of hydrated
phases during firing has a deleterious effect on
the properties of the castables. Also cement
compositions suffer due to the presence of
lime, and have therefore limited applications
at very high temperatures. Colloidal or sol
binders are devoid of these drawbacks but suf-
fer from a weaker strength at low tempera-
tures. Chemical bonds have their own bene-
fits but also have disadvantageous properties
at high temperatures. | [21] Parr, C., Revais, C., Fryda, H.: The nature of chemical
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1 Department of Ceramic Engineering, National Insti-
tute of Technology – Rourkela, Odisha, India
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