Castable Refractory Concretes

Castable refractory concretes
W. E. Lee, W. Vieira, S. Zhang, K. Ghanbari Ahari, H. Sarpoolaky, and C. Parr
Castable refractories containing calcium aluminate

cement (CAC) are used ubiquitously in a range of
furnace lining applications in the iron and steel,
cement, glass, ceramic, and petrochemical
industries. This review outlines their development
from conventional high cement materials, through
low cement and ultra-low cement castables to the
present materials which may be entirely free of
CAC. Castables are defined in terms of both CaO
content and installation procedure. Production
routes, compositions, and microstructural
evolution on hydration, setting, dehydration, and
firing are described for pure CACs and castable
refractories. The development of the low cement
systems is discussed in terms of particle packing,
dispersion, and rheology highlighting the influence
of colloidal matrix additions of silica and alumina.
Recent developments including cement free, selfflowing, shotcreting, and basic castables are
described and the potential for carbon-containing
systems evaluated.
IMR/368
1 Typical
powder
microstructure
2001 IoM Communications Ltd and ASM International.

Professor Lee, Dr Vieira, Dr Zhang, Dr Ahari, and Mr
Sarpoolaky are in the Department of Engineering Materials,
University of Sheffield, UK and Mr Parr is with Lafarge
Aluminates, Paris, France.
Abbreviations
BFA
CAC
CVC
HAC
LCC
SFC
TA
ULCC
WFA
Chemistry
A
C
F
H
M
S
T
brown fused alumina

calcium aluminate cement
casting vibration castable
high alumina cement
low cement castable
free or self-flowing castable
tabular alumina
ultra-low cement castable
white fused alumina
Al O
2 3
CaO
Fe O
2 3
HO
2
MgO
SiO
2
TiO
2
Introduction
Refractories are a group of ceramic materials used in
massive quantities to line vessels in which other
materials (such as metals, glass, and cements) are
manufactured at elevated temperatures. They consist
of large sized (up to centimetres) aggregate (filler)
phases held together with finer (sometimes submicrometres), often porous, binder phases conferring the
microstructure shown schematically in Fig. 1. Typical
aggregates include fused alumina, tabular alumina,
ISSN 09506608
processed
refractory
calcined bauxite, and sintered MgO while bonding

systems may be based on carbon derived from pyrolysed pitches and phenolic resins, mullite and glass
from decomposed clays, or alumina and calcium
aluminate phases formed from fired hydraulic calcium
aluminate cements (CACs). The most significant trend
in refractories technology in the last two decades has
been the ever increasing use of monolithics, or
unshaped refractories, which now, in many countries,
account for more than 50% of total production.
Owing to improved refractories quality their consumption has decreased dramatically in the last two
decades while the ratio of monolithics to preshaped
refractories (bricks) has been steadily increasing.16
The reasons for the rapid growth of monolithics,
at the expense of bricks, are their ready availability,
faster, easier, and cheaper installation, and fewer
corrosion-susceptible lining joints.611 The term
monolithic usually includes a wide variety of material
types and compositions, with various bonding systems, ranging from fluid cement pastes to sti plastic
lumps.6,11,12 Monolithic materials were first used as
a distinct refractory product in 1914, when the first
commercial refractory plastic, a simple blend of
crushed firebrick and fireclay, was produced.5,6,12
From this, monolithics have evolved into a versatile,
widely used class of refractory materials that oer
performance and cost eectiveness comparable, and
sometimes even superior, to those of shaped refractories. The success of monolithics is due to significant
advances in the type and quality of their binders,
aggregates, and additives as well as to innovation in
their design and installation techniques.5,6
The evolution of monolithic refractories over the
past century has been described in a recent review.13
A significant advance in monolithics technology was
the development of refractory concretes or castables
based on CACs.68,11,14 Castables are complex refractory formulations, requiring high quality, precisionsized aggregates, modifying fillers, binders, and additives.11,14 Refractory castables are dry granular materials which require water addition. Installation is by
casting or pouring into place, vibration placement,
International Materials Reviews 2001 Vol. 46 No. 3 145
146 Lee et al. Castable refractory concretes
trowelling, or projection (spraying or shotcreting).

The majority of castables contain a CAC binder,
though a few still use Portland cement.6 While conventional castables, which contain the largest amount
of cement, still make up the greatest percentage of
those produced, use of reduced cement varieties, low
cement castables (LCCs) and ultra-low cement castables (ULCCs), has grown significantly over the past
10 years.6 This is because the CaO present in the
cement leads to deterioration of high temperature
properties.
Castables or refractory concretes commonly contain bonds based on high alumina cement (HAC), a
reactive phase, or a gel. They may be cast in moulds
to form specific products (precast shapes) or cast in
place, as when forming a lining for a kiln furnace.
Dense concretes are prepared using discrete particle
sizes, with the largest up to several centimetres in
size. Mechanical vibration may be used to assist the
flow of the concrete or to enable mould filling with a
lower liquid content in the slurry. Some products are,
however, cast without vibration, and such concretes
are said to be free or self-flowing.15 Some refractory
compositions may be premixed with water and then
pumped under pressure to the site of placement,
where they are projected or sprayed on to the surface.
This process is called wet gunning or shotcreting, and
the concrete is termed a shotcreting or sprayable
castable.16 This is quite dierent from the earlier dry
gunning process where the powder and water are
mixed at the nozzle of the device used to place
the slurry.
Modern castables are used increasingly in almost
every refractory application, such as for the repair of
stacks17 and lining of iron and slag runners in blast
furnaces,2,3,7,18 torpedo ladle throats and barrels,2,1719 steel ladles2,3,7,17,18,2027 and tundish
linings,2,3,7,17,18,28 hearths, soaking pits, and skid rails
of reheat furnaces,7,17,19 nose ring and discharge areas
of rotary cement kilns,1719,29,30 direct reduction
kilns,19 coke oven door plugs,7,31 cyclones and transfer
lines of fluidised catalytic cracking unit vessels of the
petrochemical industry,6,7,17,19,29 foundry ladles and
heat treating furnaces,6,18 aluminium reverberatory
furnaces and ladles,6,7,16,19,29 boilers and waste incinerators,6,16,32 repairing of sliding gate plates,33 fabrication of monolithic porous plugs, seating (well)
blocks and powder injection lances,33 desulphurising
and argon stirring lances,29 refractory lining of snorkels in RH degassing vessels33 and, more recently,
fabrication of shrouds and submerged entry nozzles
used for the continuous casting of steel.34,35
In this review the important historical developments leading to modern castable systems (see the
section Historical evolution below) and the methods
of distinguishing the various types (see the section
Classification below) are briefly described. The production and hydration and dehydration of pure CACs
are considered before examining refractory systems
in which they are bonding phases: conventional castables, LCCs and ULCCs. The importance of particle
packing, dispersion, and rheology is highlighted as
well as the types of submicrometre powder and aggregate used. Then the modern developments of cement
free, free flowing, shotcreting, and spinel and MgOInternational Materials Reviews 2001 Vol. 46 No. 3
based systems are reviewed. Finally, the possibility of

carbon-containing castables is discussed.
Historical evolution
The first refractory concrete was made and put to
practical use by Sainte-Claire Deville, in France,
sometime before 1856.5,12,13,3638 He heated mixtures
of alumina and lime and mixed this reaction product
with corundum aggregate and water to produce high
temperature crucibles. However, the hydraulic properties of compounds formed by reacting lime with
alumina were known long before the individual calcium aluminates were isolated in a pure condition
and positively identified.36 The cementitious action of
lime had already been appreciated by the Egyptians
and Romans, who relied to some extent on the rather
slow action of atmospheric carbon dioxide to carbonate the lime and so develop the strength of their
mortars.39 This type of cementitious action, however,
is not entirely satisfactory if air is excluded as, for
example, in underwater construction.
The next notable advance in cement development
stemmed from the work of John Smeaton, around
1756, who recognised that the calcination of certain
selected limestones would give powders with
hydraulic setting properties. In the 1840s, following
the works of L. G. Vicat (1846) in France and Joseph
Aspdin in England, these natural cements, as they
were called, were superseded by Portland cement, a
calcium silicate product prepared by calcining to a
(partially melted) clinker a wet ground mixture of
limestone and clay.12,39
The development of the first CACs stemmed from
the shortcomings of calcium silicate cements exposed
to the action of ground waters containing sulphates.39
In the second half of the 19th century many patents
were granted on methods for making calcium aluminate type cements by combining lime with bauxite.
However, it was not until 1918 that the Lafarge
Company in France, based on a patent by Bied in
1908, began to sell a CAC, marketing it as a sulphate
resistant product for sea water corrosion resistant
concrete.5,37,38 Production was based on the use of
cupolas or small blast furnaces which were top-fed
with a mixture of high iron bauxite, limestone, and
coke, and from which pig iron and an aluminous slag
were tapped separately at the bottom. The slag on
grinding to powder gave high alumina cement.39
Despite the early work of Deville, it was not until
the mid-1920s that the high temperature properties
of CAC were fully appreciated. Before that, calcium
aluminate was often seen as an alternative to Portland
cement and no mention was made of its potential in
refractories applications. In 1924, the Universal Atlas
Cement Division of the US Steel Corporation began
manufacturing a CAC for use as a binder in refractory
mixes.5,38 In 1929, refractory castables bonded with
CAC were already manufactured industrially in the
USA, while production in Japan commenced in
1939.12,37 During the early days of refractory concretes, the main aggregates available for use were
calcined clays and crushed fired refractory bricks.
Tabular alumina, although available in the 1940s, was
not then widely used in monolithic refractories, pre-
Lee et al. Castable refractory concretes 147
sumably because of its relatively high cost. The concretes were crudely made and even more crudely
applied. Mixing was commonly done by hand in a
mortar box or wheelbarrow, and casting, slap trowelling, and hand forming were the most common early
forms of installation, though some gunning was also
done.5
In the 1950s, following experiments made with
purer raw materials, Alcoa and Lafarge began marketing high purity CACs specifically developed for the
refractories industry, resulting in a wide range of
HACs produced from mixtures of pure alumina and
limestone and containing small amounts of silica and
iron oxide.5,38,39 By 1960, castables based on high
purity CAC and tabular alumina aggregates were
common, claiming advantages in the areas of refractoriness, erosion, and abrasion resistance.5,40
However, these had relatively simple compositions,
consisting of refractory aggregates and cement, the
latter added in sucient amounts to give suitable
room temperature strength.18 The major disadvantages of these conventional castables, containing as
much as 30%* cement, were the high water content
required for placement, which increased the porosity
and lowered the strength of the material, their loss of
strength during the dehydration process, and the
sharp drop in strength at high temperatures due to
the fluxing action of CaO.7,18,33,37 Improvements in
this product were largely due to higher purity cements
and aggregates, while the base technology stayed
the same.41
In the late 1970s, reduced cement materials based
on the Prost patent of 1969 were manufactured.18,29,37,4247 These LCCs contained at most
25% lime, achieved by dramatically reducing the
amount of cement binder, which is partially replaced
by fine oxide particles, and distributing it evenly
within the mix, with the aid of deflocculants and
similar additives. The grain size distribution of the
aggregates was also altered so that the interstices are
progressively filled by smaller grains to obtain maximum packing density, which also increases the
amount of water utilised in flow. Later, ULCCs,
characterised by an even lower lime content (<10%)
were developed. Low and ultra-low cement castables
have uniform microstructure with low porosity and
high strength throughout the low and intermediate
temperature range, and a low lime level that improves
high temperature strength and corrosion resistance.15
In the last two decades they have successfully replaced
a variety of other monolithics, such as conventional
high cement castables, plastics, ramming and gunning
mixes, as well as many brick compositions.
Following the success of LCCs and ULCCs and
the appreciation of the rheological properties of saturated systems, a new family of refractory concretes
was developed in the mid-1980s, free or self-flowing
castables (SFCs).15,31,48,49 These are LCCs or ULCCs
with a consistency after mixing that allows them to
flow and degas without application of external
energy.48 Self-flow technology also paved the way for
a new placement technique, referred to as wet gunning, shotcasting, or shotcreting. Although the charac*All percentages are wt-% unless otherwise stated.
teristics of shotcreted LCCs were first published in

1986, it was not until after the advent of the selfflowing technology that wet gunning became a more
eective installation tool. Pumping self-flow mixes
over significant distances, both horizontally and vertically, enabled the technology to evolve to include wet
gunning.16
Nowadays, refractory concretes are available which
contain low, intermediate, or high purity CACs in
large (conventional), small amounts (low and ultra
low), or none at all (non-cement, cement free), combined with a wide variety of organic and inorganic
additives, such as deflocculants, setting retarders and
accelerators, and aggregates such as calcined clays
and bauxites, tabular and sintered aluminas, white
and brown fused aluminas, sintered and fused magnesia, chrome ore, zircon, kyanite, mullite, silicon
carbide, aluminamagnesia spinels, and fused silica.
Cement free castables are used in numerous molten
iron and steel contact applications, where the elimination of lime in the refractory matrix improves high
temperature behaviour. Such castables use a variety
of bonding mechanisms. Bond systems used include
clay bonding, gel bonding, hydratable alumina bonding, and phosphate bonding. Other additions to castables include the use of stainless steel fibres and
organic bake-out fibres, the first to prevent damage
from thermal shock, and the second to increase
permeability to allow water removal during the dehydration period.14,50
Classification
Refractory castables are classified by the ASTM
according to their lime content into conventional
(CaO>25%), low cement (25%>CaO>10%),
ultra-low cement (10%>CaO>02%), and cement
free (CaO<02%).14,30,38 According to this classification, castables containing up to 1% high alumina
(80% Al O ) cements may fall into the last category,
2 3
despite the presence of some cement. These definitions
can be misleading, and have led to the introduction
of new types of so-called cement free castable made
up of a mixture of cement and other bonding agents,
such as r-alumina.51,52
Castables can also be classified by installation
method as casting vibration castables (CVCs) and
self-flowing castables (SFCs).31 Shotcreting castables
are SFCs but because not all SFCs are suitable for
pumping and wet gunning, particularly those with
dilatant behaviour,16 these castables should also be
separately classified. Also, it is possible that a vibratable castable will become self-flowing if more water
is added to the mix, or vice versa, and therefore, in
some cases, the classification of castables with no
mention of the amount of water required for installation is meaningless. Attempts have been made to
classify castables according to the nature of the dispersing phase, i.e. inorganic or organic.31 However, this
is also meaningless, since modern high performance
materials may include a combination of several additives, both organic and inorganic in nature.
Classification of modern castables is dicult.
However, a proper classification should include as
much information as possible about the chemical
International Materials Reviews 2001 Vol. 46 No. 3
nature, rheological behaviour,

characteristics of the castable.
and
installation
Calcium aluminate cements

Despite the steady decrease in the amount of cement
used in modern high performance refractory castables,
CACs, particularly high alumina cements, continue
to be the most important hydraulically setting agents
used for bonding concretes,53,54 mainly because they
develop high strength within 624 h of placement.
Usually, high alumina castables require only 24 h to
develop 7080% full strength when properly cured,
in contrast to 28 days for normal Portland cement
concretes.53 Calcium cements are usually classified
according to purity and Al O content. In 1972,
2 3
Briebach39 classified them in four major groups
(Table 1). Only cements in Group 2 were referred to
as high alumina cements, while those in Group 4
were often called white high alumina cements,
because of their colour. Today, however, any calcium
cement from Groups 2, 3, or 4 is often termed CAC
or high alumina cement (HAC), or simply calcium
aluminate (CA).38,53
A more recent classification of HACs38,53 is given
in Table 2. Relatively pure limestone (5455%CaO,
4143% loss on ignition, and less than 2% total
impurity) is used as the lime source for producing all
CA cements. The low purity cements (LP CAC) are
manufactured from bauxites containing up to
~18%Fe O and 9%SiO . Low iron (24%Fe O )
2 3
2
2 3
and low SiO (57%) bauxites are used to manufac2
ture the intermediate purity cements (IP CAC), while
Table 1 Classification and composition of calcia
containing cements
Cement group
Mineral
Calcium
silicate
Calcium aluminate cements
Portland
High alumina
Chemical analysis, wt-%

SiO
1726
49
2
Al O
512
3545
2 3
Fe O
1727
1015
2 3
CaO
5365
3639
...
White high
alumina
46
5065
13
2940
0114
6580
0110
1725
Table 2 Classification and properties of calcium

aluminate cements
Type
Low purity
Intermediate purity
High purity
Chemical analysis, wt-%

SiO
2
Al O
2 3
Fe O
2 3
CaO
4.590
3950
716
3542
3560
5566
13
2636
0003
7090
0004
928
Surface area, m2 g1
Wagner (ASTM C115)
Blaine (ASTM C204)
BET
014016
026044
060100
016024
032100
080500
022030
036150
0601800
305325
3:009:00
295310
3:0012:00
300330
0:306:00
Density, g cm3
Vicat initial set, h5min
(ASTM C191)
calcined alumina is often the choice for the high

purity type (HP CAC).
Alternatively, cements or CACs may be classified
according to chemical composition, forming five main
groups (Table 3).12 In Table 3, Group A includes
fondu and lumnite cements, while Groups B and C
include the two alumina cements for refractories
specified in the Japanese Industrial Standards. Group
D includes high purity alumina cements of the
70%Al O class, such as the Denka high alumina
2 3
cement and Secar 71 (Lafarge). High purity alumina
cements with ~80%Al O , such as the Denka super
2 3
high alumina cement, CA25 (Alcoa), and Secar 80
(Lafarge) are typical of Group E. An important
variable in these commercial cements is admixture
content, e.g. Secar 71 is additive free while Secar 80
(like all 80% alumina cements) contains a cocktail of
additions which will confer consistent properties on
the cement but will influence rheology in a castable
system based on this cement.
Production techniques
Calcium aluminate cements are formed by reaction
of lime and alumina either by a sintering or clinker
process or from fusion.12,38 In the latter limestone
and bauxite raw materials are melted at 14501550C
in reverbatory furnaces fired by powdered solid fuel.39
The molten calcium aluminate is continuously tapped,
cooled, and ground into cement. Other melting processes involve the use of vertical shaft and rotary
kilns, while electric arc resistance furnaces have also
been used where electrical energy is relatively cheap.38
In this process the proportioned dry raw mix of Bayer
Al O and limestone is either fed as ground or as an
2 3
agglomerate into a rotary kiln, similar to that used
in the manufacture of Portland cement. The product
is sintered at 13151425C, cooled, and then ground
to cement fineness together with any additives. These
include calcined alumina to obtain the desired Al O
2 3
content, gypsum or other materials to control the set,
and plasticisers to improve workability.38,53 The
cement colour ranges from black to white, depending
on the impurities present and on the iron oxide
quantity and oxidation state. High purity cements
are white.
On sintering, the raw mix generally transforms into
higher alumina phases as the material temperature
increases in the kiln. Both lime/alumina ratio and
temperature determine the amount and type of calcium aluminate phases formed during the process.
High lime calcium aluminates form initially with
ferrites and silicates. Uncombined lime and alumina
begin to react with the high lime products and form
lower lime or higher alumina compounds, as predicted
by the CaOAl O binary phase diagram (Fig. 2).
2 3
These reactions continue in the kiln until the mix is
completely combined as follows38
C+AC AC A CACA CA
3
12 7
2
6
High purity CAC sinters readily, even though very
refractory high purity limestone and Bayer calcined
alumina are used as raw materials in rotary kiln
calcination. A 1360C eutectic occurring at
~50 wt%CaO/Al O (Fig. 2) enhances liquid phase
2 3
sintering of these refractory oxides.

Table 4 Typical mineral constituents of calcium
aluminate cements
Relative
hydration rate
Fast
Moderate
Slow
Non-hydrating
Cement purity
Low
Intermediate
High
C A
12 7
CA
CA
2
C S
2
C AF
4
C AS
2
CT
A
C A
12 7
CA
CA
2
C S
2
C A
4 F
C AS
2
CT
A
C A
12 7
CA
CA
2
...
...
CA
6
A
...
highest strength among the phases listed during the

relatively short time available for hydrating refractory
concretes. It takes some time to start setting, but
hardens rapidly after the initial set.
Calcium dialuminate (CA ) is the secondary phase
2
in CACs (<25%) and is more refractory than CA but
takes an excessively long time to set though accelerated at high temperature.38 While hydration of CA
is known to be accelerated by the presence of CA ,
2
the opposite does not hold true, and the hydration of
CA may actually be hindered by the presence of
2
CA.55 The strength of CA after three days hydration
2
is comparable to that of the pure CA and, unlike in
CA, it always increases with time.
C A hydrates rapidly and can be used to control
12 7
the setting rate of CACs when used in small quantities;
it has a relatively low melting point. C S and C AF
2
4
are common in Portland cement, but can also occur
in the high silica and iron rich low purity CACs,
respectively. C AF forms hydrates of calcium alumin4
ate and calcium ferrite or solid solutions of the two
hydrates, and in its setting rate it resembles C A
12 7
(Ref. 12). C AS (gehlenite) shows little tendency to
2
hydrate and is an undesirable component of alumina
cement which limits refractoriness and hot strength
properties.38
CA is the only non-hydrating phase in the pure
6
calcium aluminate system and is often a reaction
product in alumina castables bonded with high purity
aluminate cement. It is believed that CA is most
6
readily formed in alumina castables when using CA
2
as a precursor.56 More recently, studies on the properties and microstructure of the CA phase have
6
revealed its great potential as a strong thermal shock
resistant, refractory material38,57,58 and its important
role in the bonding of corundum and spinel
aggregates.40
2 Binary CaOAl O phase diagram; in wt-%

2 3
The two most critical areas of cement production

are development of the clinker phases and the grinding process. Not only are the amount and proportions
of clinker phases important, but also their reactivity.
The crystallinity of a cement phase is important in
controlling cement reactivity. It has been shown,
for example, that C A , generally considered an
12 7
extremely reactive phase of the sintered clinker, can
be rendered quite unreactive when present in the
fused form.45 Control of the particle size on grinding
is important, because variations in the particle size
distribution can not only aect cement hydration, but
also its reactivity with the aggregates in the concrete.
Phase composition
Typical phases present in commercial CACs, according to their relative reaction rates with H O (Refs.
2
38, 53) are listed in Table 4. They form the hydrated
cement phases responsible for developing strength
after curing the concrete in a humid environment.
Useful properties of these minerals are listed in
Table 5.
Monocalcium aluminate (CaO.Al O or CA) is the
2 3
most important component of CACs because it generally occurs in large amounts (4070%), has a relatively high melting point (1600C), and develops the
Table 3 Chemical composition (wt-%) of commercial alumina cements

Group
A
Composition
10
SiO
2
TiO
2
Al O
2 3
Fe O
2 3
CaO
MgO
Na O
2
KO
2
Loss on ignition
305
195
4211
1555
3746
065
008
005
021
829
208
4134
1132
3524
117
010
009
080
472
216
4755
952
3482
119
006
002
035
459
209
5228
534
3527
035
010
005
005
252
323
5669
089
3575
043
008
011
007
341
249
5621
188
3539
053
008
004
015
019
Tr.
7336
035
2446
030
018
004
043
020
Tr.
7107
009
2770
033
021
002
017
008
Tr.
8022
015
1763
035
066
Tr.
106
020
Tr.
7953
022
1712
044
051
007
144
Generally, the characteristics of CACs are associated with the amount of alumina, lime, and impurities
present in the products. Increased alumina content
will confer higher refractoriness, while a high lime
content in the cement increases cured strength. Iron
impurities lower the carbon monoxide resistant at
high temperatures, and siliceous compounds reduce
resistance to hydrogen atmospheres under similar
conditions.38
Hydration
The hydration mechanisms of CACs have been studied extensively (e.g. Refs. 8, 5965). However, systematic structural studies of cements are dicult. Starting
materials and hydration products are typically multiphase systems, which are, because of the occurrence
of metastable phases, often compositionally variable,
sensitive to experimental conditions, such as temperature, duration, and intensity of mixing, and typically
only partially crystallised. For these reasons, identification and quantification of all of the chemical phases
present in cements is not always possible.66
Figure 3 shows reaction schemes for hydration of
CA, CA , and C A . When any cement is mixed
2
12 7
with water the hydraulic minerals begin to dissolve
quickly forming a saturated solution of ions. In CACs
Ca2+ and Al(OH) ions form. Nucleation of
4
hydration products and their subsequent crystal
growth produces an interlocked network that gives
setting and then strength.65 Rates of hydration are
a strong function of the starting CaO/Al O (C/A)
2 3
ratio and temperature. The hydration of CA occurs
through initial dissolution and subsequent precipitation of CAH and C AH from the supersaturated
10
2
8
solution. An induction or incubation period occurs
before this precipitation and is a reflection of the
nucleation barrier.67
Hydration starts with contact of cement with water.
Initial attack of the anhydrous phase particle surfaces
produces a layer of hydrated calcium aluminate and
a layer of apparently amorphous aluminium hydroxide. In the induction period, the hydration rate is
extremely low, and the thickness of the hydrated
surface layer grows slowly. When the hydration layer
reaches a critical thickness, the stress caused by
intruded water molecules ruptures the layer and the
induction period terminates (the reaction as a whole
accelerates) with the formation of crystalline nuclei
that grow by a dissolutioncrystallisation mechanism
to produce the metastable hexagonal hydrate CAH .
10
Depending on the initial crystallinity of the aluminate,
(a)
(b)
(c)
3 Reaction schemes for a CA, b CA , and c C A

2
12 7
(after Ref. 63)
CAH can be detected after 624 h. The presence of

10
C AH can be detected after 24 h.
2
8
The hydration of calcium aluminates has been
extensively studied using a variety of methods, includ-
Table 5 Properties of CAC mineral constituents

Chemical composition, wt-%
Mineral
C
C A
12 7
CA
CA
2
C S
2
C AF
4
C AS
2
CA
6
a-A
998
486
354
217
651
462
409
84
...
...
514
646
783
...
209
372
916
998
...
...
...
...
...
329
...
...
...
...
...
...
...
349
...
219
...
...
T , C
m
2570
14151495
1600
17501765
2066
1415
1590
1830
2051
Density,
g cm3
Cold crushing
strength,
MPa
Setting time,
h5min
Initialfinal
Crystal
system
332
269
298
291
327
377
304
338
398
...
15
60
25
...
...
...
...
...
...
0:050:07
7:008:00
18:0020:00
...
...
...
...
...
Cubic
Cubic
Monoclinic
Monoclinic
Monoclinic
Orthorhombic
Tetragonal
Hexagonal
Rhombohedral
% CONVERSION
C2AH8+AH3
C3AH6+
2AH3
TEMPERATURE, C
5 Temperature dependence of calcium aluminate

hydrates formation (after Ref. 65)
4 Typical curve for evolution of heat in calcium
aluminate cement
ing solution chemistry,6870 X-ray diraction,71,72

calorimetry,62,7375 1H NMR (nuclear magnetic resonance) relaxation rates, and continuous wave 27Al
NMR spectroscopy.61,66,75
The hydration of cement is an exothermic process,
and the heat of hydration evolved can be easily
detected by means of isothermal conduction calorimetry (ICC). Adiabatic calorimetric studies of calcium aluminate cements with water show two
exothermic peaks, as illustrated in Fig. 4.76 The first
occurs immediately on contact with water, due to the
heat of wetting and the rapid dissolution of cement
to form a solution saturated in lime and alumina.77
The first peak is also believed to be associated with
the formation of the first reaction layer on the grains
of the hydraulically active substances.62 The dormant
(induction or incubation) period then follows, during
which hydrate nuclei form and develop. It has been
observed that from 25 to 70C the length of the
induction period decreases with increasing temperature.61 Once critical nuclei have been formed, massive bulk precipitation of hydrates occurs, giving rise
to a second major exothermic peak, and initiating the
hardening process.
Evolved heat of hydration diers widely depending
on the type of cement and its mineral constituents.
As indicated by Table 6, most of the hydration reactions in CACs end in a short period of time and the
amount of heat liberated by these cements over one
day approximately equals that liberated by Portland
cement over 28 days.12 The evolution of heat during
hydration is greatly aected by temperature, and the
amount of heat evolved increases with the ambient
temperature. The time needed to reach the maximum
rate of heat evolution, after water addition, is also
aected by temperature, and so is the setting time.
The longest time required is usually at about 30C.
The factors influencing the evolution of heat and
setting time of CACs, particularly around 30C, are
not yet fully understood.78 After setting, the strength
Table 6 Heats of hydration of Portland and CA
cements, cal g1
Time, days
Cement
28
CA cement
Portland cement
7793
2346
7894
4265
7895
4775
...
6694
of the cement increases rapidly. The evolution of heat

and the development of strength in CACs are related
to each other, both stemming from the hydration
reactions.12
Recent NMR studies indicate formation of an
intermediate product, which could be forming directly
from the surface hydrated layer or, alternatively, by
dissolution and reprecipitation. It has been suggested
that the end of the incubation period and the start of
the main reaction period, which is followed by massive
precipitation, are actually due to the formation of
this material.61
Depending on the water/cement ratio, curing conditions, and the presence of impurities, dierent
hydrated products may form during the process. In
particular, the hydration process varies with curing
temperature8,12 and the use of additives, such as
setting retarders and accelerators.66 In castables, the
hydration of cement can be additionally altered by
the presence of impurities in the aggregates such as
Na O (Ref. 74) and microsilica additions.45,59,64,79
2
The stable hydration products formed from the initial
sintered mineralogical phases and their crystalline
structures generally develop within 36 months under
ambient conditions, or within the first 24 h if curing
is performed at higher temperature. The following
reactions take place when CAC and water are combined8,12,38,65
<21C CAH10 (metastable hexagonal)
CA
AH
C A
3
12 7
2135C
CA +H CA
CA
(1)
(gel)
(2)
C AH (metastable hexagonal)
2
8
C
AH
(stable cubic)
>35C
3
6
(3)
CA
AH
(crystal)
3
As the temperature rises above 21C, the metastable

hydrates CAH and C AH change into the more
10
2
8
stable compounds, C AH and AH .8,12 The tran3
6
3
sitional crystalline change from one calcium aluminate hydrate to another is commonly referred to as
conversion. Figure 5 summarises the changes in principal hydration product with curing temperature.
The morphologies of the main CAC hydrates (listed
in Table 7) vary extensively though in general C AH
3
6
forms as cuboids, C AH as platelets, CAH as
2
8
10
needles or hexagonal prisms, and gibbsite as tablets
or needles. Figure 6 shows the C AH and C AH
2
8
3
6
morphologies developed in the fine matrix CAC of
an LCC system.80 Direct formation of the denser
Formation of stratlingite avoids the conversion reaction and may, therefore, lead to superior low and
intermediate temperature strength and stability.
Furthermore, the presence of other forms of alumina
also influences hydration and rheological properties.83
The surface area, Na O content, and releasability of
2
the aluminas are particularly important and can have
an eect on the high temperature microstructural
development, see the section Calcined alumina
below.
a 18 h, C AH hexagonal plates; b 11 d, C AH deltoid icositetrahedra

2 8
3 6
6 Hydrate microstructure in CAC with water/

cement ratio 2 at ambient temperature;80
marker 10 mm
stable hydrates (AH and C AH ) at higher curing

3
3
6
temperatures produces greater porosity and larger
pore sizes than when the metastable and less dense
hydrates (CAH and C AH ) are formed at lower
10
2
8
temperatures. While this gives lower green strengths65
it also gives coarse, permeable hydrate phases so that
vapour species can escape on drying. The impermeable AH gel phase developed at low curing tem3
peratures increases the danger of explosive spalling
on drying due to steam build up. For this reason,
refractory CAC castables are generally cured above
27C. Best practice for safe heating and maximum
strength development is to cure for at least 24 h at
3038C covered in an impermeable membrane to
maintain a humid environment for hydration, followed by a 24 h air cure with the surface exposed to
3038C.81 The increase in porosity and its eect on
strength are also heavily influenced by original total
water/cement ratio.
The presence of other phases such as microsilica
or reactive magnesia along with CAC in castables is
known to influence the hydration mechanism.64,82
Pantjadarma64 determined that stratlingite (gehlenite
hydrate, C ASH ) formed with microsilica present
2
8
having the same platey morphology as C AH sug2
8
gesting it formed by reaction of silica and C AH .
2
8
Table 7 Properties of CA cement hydrates
Chemical composition, wt-%
Hydrate
CaO
CAH
10
C AH
2 8
C AH
3 6
AH
3
166
313
444
...
Al O
2 3
301
284
270
654
HO
2
535
403
286
346
Crystal
system
Density,
g cm3
Hexagonal
Hexagonal
Cubic
Hexagonal
172
195
252
242
Additives
Chemical additives or admixtures are used to control
the reactivity of the cement. These are ground and
blended with the cement during the manufacturing
process to control or modify the properties of the
binder.38 The use of such admixtures in castables is
considered by many45 unacceptable because most
formulations incorporate deflocculants and buers to
control the rheology of the product and the addition
of admixtures to the cement can alter the properties
of the castable by interacting with these additives.
Besides those additives used for dispersion, see the
section Submicrometre (superfine) matrix additions
below, the most common additions to calcium aluminate containing castables control the setting characteristics of the cement. They are the so-called set
retarders and accelerators. Among the retarders, the
following are significant: citric8486 and phosphoric8
acids, diluted acetic acid,38 boric acid,60,87 borax,8,38
sodium citrates60,88 and gluconates,60 hydroxycarboxylic acid salts,8,38 saccharides,8 magnesium and
barium hydroxides,38 sodium chlorides and sulphates,38 starch, sugar, sea water, and many other
acids and acidic compounds.38 The most commonly
cited set accelerators are: lithium salts and carbonates,38,88
calcium
hydroxide,38,60
Portland
cement,38,51 slaked lime,66 hydratable aluminas,51
sodium and potassium carbonates,38 sodium silicates,38 and many other alkalis and alkaline compounds.38 It has been suggested88 that the combined
use of set retarders and accelerators is more eective
and allows better control of the hydration process.
The reaction mechanisms of set retarders and accelerators are still unclear,8 but it is generally agreed
that retarders influence the kinetics of hydration by
slowing down the dissolution of the anhydrous cement
particles.89 It is believed that accelerators influence
mainly the dormant period of hydration. Lithium
salts are mostly used as accelerators, and it is believed
that lithium ions interact with Al(OH) to precipitate
4
insoluble lithium aluminate hydrate, thereby increasing the Ca2+/Al(OH) ratio in the solution. Rapid
4
hydrate formation is then promoted, and the setting
time is consequently reduced.89
Dehydration and firing
Strength loss is known to occur in hardened calcium
aluminate pastes as the metastable hexagonal CAH
10
phase dehydrates through the hexagonal C AH
2
8
transition phase into the stable cubic C AH .12,38,51,90
3
6
This loss of strength can best be appreciated by
considering the morphological and volume changes
accompanying this conversion. When CAH
is
10
allowed to form during low temperature curing, the

metastable hexagonal prisms (density 172 g cm3)
and gel (242 g cm3) solidify and eventually will
convert to the stable cubic (252 g cm3) type with
time and/or temperature. The gross restructuring
from H O loss leading to pore formation and nominal
2
50% volume shrinkage on conversion of CAH to
10
the denser C AH and a-AH are disruptive to a rigid
3
6
3
structure and account for the observed loss in
mechanical strength.
As the temperature is increased, the dehydration
process continues, until all phases lose their water of
crystallisation. Dehydration temperatures may be
measured by thermal analysis techniques, such as
dierential thermal analysis (DTA), derivative thermogravimetry (DTG), and dierential scanning calorimetry (DSC). The dehydration is also a complex and
not fully understood process. CAH loses part of its
10
water of crystallisation at temperatures lower than
indicated by thermal analysis (5070C). Part of this
water of crystallisation is even lost at low humidity
at room temperature and, since CAH is sometimes
7
formed, it is believed that CAH may have three
10
water molecules that are easily dehydrated. Such
unstable hydrates are expressed as CAH (x<10).
x
C AH , in its turn, often shows a stepwise dehy3
6
dration process, usually indicated in the DTA curve
by two endothermic peaks, one around 300C and
the other close to 500C. It has been claimed that the
first 45 molecules of water are lost in one step, and
the next 15 in another.91 The possibility that the
15H O phase (C AH ) might represent some inter2
3
15
mediate stage or compound had been suggested.92
However, more recent studies indicated that the
C AH is merely a metastable structural relict which
3
15
constitutes a step in the dehydration of C AH at
3
6
low partial pressures of water.93 AH gel and gibbsite
3
usually dehydrate between 210 and 300C (Table 8)
but they may otherwise convert to boehmite (AH),
which only dehydrates at ~530550C.
The compounds formed during hydration of CACs
dehydrate up to ~550C.12 The process of hydration,
followed by dehydration, creates the anhydrous
material which is extremely fine and active.36 Lime
and alumina reappear and recombine in a way similar
to that of the original raw materials in the kiln.38,94
Table 9 depicts the mineralogical changes in HACs
as the temperature increases up to 1500C.12 The
microstructural changes associated with these reactions and the morphologies of the phases formed were
studied in detail by Parker.95 She determined that on
drying at 110C, CAH and C AH either dehy10
2
8
drated to amorphous products or, if water was present, converted to C AH and gibbsite. Firing above
3
6
300C dehydrated the pastes completely and reduced
their strength due to increased porosity and pore
growth. Pastes fired to 900C and dried pastes were
morphologically similar while above 900C CA crystallised and sintering began to occur leading to
Table 8 Dehydration temperature of CA cement
hydrates
Hydrate
Dehydrating temperature, C
CAH
10
100130
C AH
2 8
170195
C AH
3 6
300360
AH
3
210300
coarser pores in the plates and cuboids which subsequently collapsed. Sintering led to ceramic bonding
and improved strengths.
Conventional castables
Conventional castables consist of graded refractory
aggregates bonded with the aluminous hydraulic
cements described in the section above. The properties
of these concretes depend largely on the choice of
refractory aggregate and hydraulic cement.19 They
contain ~1530%CAC,18,29,33,37 this amount being
necessary to achieve satisfactory strength at low and
intermediate temperatures though it makes the material thirsty. The 815% water generally added during
processing is mainly used to develop the hydraulic
cement bond (610%) and to make the concrete flow
(26%), allowing its proper installation. However, a
relatively large amount of water (05%) is often taken
up by the porosity of the aggregates and does not
contribute to the hydraulic bond.
Microstructural development
All the reactions on hydration/dehydration/firing
described for CACs in the section Dehydration and
firing above, occur in refractories in which they
are the main component of the bond system but
complicated by the presence of the various
additives/admixtures in the bond system. These may
react with the cement and eect its hydration, setting,
and firing behaviour. An additional complication is
the presence of the aggregates which increase water
requirements and may react with the bond system at
higher temperature.
All CAC hydrates in the bond phase decompose to
the calcium aluminates (C A , CA, and CA ) and
12 7
2
eventually, if enough free alumina is present, CA
6
(Fig. 7). At room temperature alumina gel, hydrated
calcium aluminates, and free alumina coexist.96 On
heating to 200C dehydration occurs and by 400C
C A starts to form from amorphous dehydrated
12 7
calcium aluminates. At 900C elongated CA forms
(Fig. 7a) from reaction of alumina and C A . At
12 7
10001200C CA reacts with alumina to form coarse
and globular CA (Fig. 7b) while at >1300C CA
2
2
reacts with alumina to form hexagonal platelets of
CA (Fig. 7cf ). This morphology is believed to assist
6
physical interlinking of the microstructure improving
high temperature strength.
Disadvantages
These high cement castables have three major
disadvantages.7,18,19,29
First, because they need so much water they are
usually porous and open textured, which greatly
reduces the strength. The low porosity and permeability of castables at temperatures below 21C is
ascribed to the alumina gel formed upon curing.53
The open porosity of a conventional castable dried
at 110C is generally about 917%,33 but can be as
low as 8%.18 Although some of this porosity is due
to entrapped air bubbles, most of it is caused by the
excess water added on mixing. On heating, the
hydraulic bond is first modified, as conversion takes
a 900C; b 1200C; c, d, e 1300C; f 1400C
7 Microstructural evolution on firing conventional castable matrix96
place, and then destroyed by the dehydration process.

During this textural modification, the pore size distribution changes and porosity grows significantly. The
new porosity depends on the amount of chemically
bonded water and is therefore dependent on cement
type and content. The final open porosity of conventional refractory concretes fired at 1000C generally
varies from 22 to 26%, depending on the type of

aggregate used.
Second, conventional castables show a characteristic drop in strength at intermediate temperatures
(often quoted to be between 538 and 982C7), when
the hydraulic bond has already broken down, due to
the dehydration process, but the still sluggish sintering
Table 9 Mineralogical changes of dehydrated high alumina cement on heating

Temperature,
C
500
600
700
800
900
1000
1100
1200
1300
1400
1500
70%Al O CAC
2 3
C A
CA
12 7
X
...
X
...
X
...
X
...
X
X
X
X
...
X
...
X
...
X
...
X
...
X
CA
CA
...
...
...
...
X
X
X
X
X
X
X
...
...
...
...
...
...
...
...
...
...
...
X
X
X
X
X
X
X
...
...
...
...
80%Al O CAC
2 3
C A
CA
12 7
...
...
...
...
X
...
X
X
X
X
...
X
...
X
...
X
...
X
...
...
...
...
CA
2
...
...
...
...
X
X
X
X
X
X
X
CA
...
...
...
...
...
...
...
...
...
X
X
A
X
X
X
X
X
X
X
X
X
X
X
has not yet allowed the development of a ceramic

bond. The exact temperature range when strength
deteriorates is not absolute, but may depend on
various factors, such as the type and proportion of
hydrates, the curing temperature, and heating schedule. C AH becomes thermodynamically unstable
3
6
above ~292C but its dehydration is a stepwise
process. In practice, higher temperatures may actually
be necessary for the complete dehydration of the
hydrates, since heating increases water vapour pressure, particularly inside closed pores, further delaying
the dehydration process. Although some hydrates
dehydrate rapidly others, such as micas, clays, and
C A H , may be heated for days or weeks at temper4 3 3
atures several hundred degrees above their equilibrium stability limit without much eect.93 Thick
(tens of centimetres) linings may develop hydrothermal pressures that can form C A H and boehmite
4 3 3
(AH).97 Although decomposed hydrates may start to
react with alumina aggregates at temperatures as low
as 900C, significant sintering of calcium aluminate
crystallites themselves and with neighbouring alumina
crystals only occurs at temperatures close to 1100C.94
Early attempts to accelerate the formation of a ceramic bond generally consisted in making additions of
various fluxes, most of which did little good and
usually reduced the maximum temperature of use.36
Values for the cold crushing strength of conventional
refractory castables fired at 1000C usually vary from
10 to 30 MPa, averaging ~60% of the strength after
drying.19
Finally, the high lime content of these castables
favours formation of a fluid vitreous phase at high
temperature via the eutectic liquid in the CaOAl O
2 3
SiO (CAS) ternary system which may encourage
2
crystal formation (e.g. mullite or spinel, see the sections Microstructural evolution on drying and firing
and Spinel and magnesia based castables below) but
often will remain as a glass (Fig. 7e) or low melting
anorthite and gehlenite on cooling which degrades
refractoriness and corrosion resistance.96,98 The
volume of viscous phase in a refractory castable for
a given temperature and refractory aggregate is
mainly determined by the impurity content of the
binding phase, i.e. by the composition and amount of
cement used. Even with a high purity CAC containing
7080%Al O , it is impossible to reduce the CaO
2 3
content of conventional castables to less than 3%,
which is still a high amount, particularly if silica
containing aggregates are used. Further reduction is
only possible by reducing the cement content.
Unlike fired refractory bricks, whose final properties are largely fixed before reaching the user, a
refractory concrete has properties which evolve and
alter for a considerable time after it has been put into
use. In the case of refractory concrete it is the behaviour at the service temperature which is more important than the unfired strength.36 By the end of the
1960s, there was little doubt about what should be
done to improve the performance of refractory castables. Reducing the amount of cement without spoiling other properties of the material proved dicult
and challenging, but after several attempts it finally
led to the development of a new range of products:
the low and ultra-low cement castables.
Low cement castables and ultra-low

cement castables
First attempts to improve the performance of
hydraulic castables by reducing water and cement
content were largely unsuccessful, since the mechanical resistance was insucient for compositions with
less than 10% cement.33 Refractory castables with no
more than 58% cement, characterised by excellent
cold and hot strengths, were first mentioned in a
French patent granted in 1969 to Prost and Pauillac.46
Reduction of the cement content without any
reduction in strength was accomplished by the
addition of ~254% fine (<50 mm, but ideally less
than 1 mm) clay minerals and 001030% deflocculants (such as alkali metal phosphates and carbonates). The objective was to reduce the amount of
water by promoting a homogeneous distribution of
the cement so that the hydraulic bond could be fully
utilised. Despite their lower porosity and better corrosion resistance, compared with conventional castables, the first generation of LCCs was too sensitive
to rapid heating, mainly because the chemically
bonded water was released in a much narrower
temperature range.29,33,37 This led to explosive spalling since the outer layers closed o and internal
water pressure built up. Further improvements led to
the development of concretes characterised by a
pseudozeolithic bond, which releases the chemically
bonded water slowly between 150 and 450C, rather
than within a narrow temperature range.29,33,99 This
minimised the problems associated with explosions
during heating but, because LCCs and ULCCs are
dense materials with low permeability, baking out is
always dicult, especially in thick installations.14
Two other French patents in 1976 and 197747
further reduced the cement content of the castables
to less than 3%, again by using dispersing additives,
such as sodium tripolyphosphate (001005%), and
fine particles. Part of the cement was replaced by fine
particles ranging from 10 to 1 mm, but the decisive
step was the use of submicrometre particles ranging
from 01 to 001 mm, which could be easily dispersed
in water without forming a sol or a gel. The idea was
to reduce the water requirement by eliminating the
intergranular voids, which are often filled with excess
water during the castable placement. This was
accomplished by carefully grading the particle size
distribution, so that interstices were progressively
filled by smaller particles to obtain the maximum
packing density.11,33,99 Water requirements were
further reduced by proper selection of deflocculants
and water reducing agents, which prevented coagulation of the fine powders and improved dispersion.
The reduction in the water content required for
vibration casting and maximising of the packing
density means these materials have high density, low
porosity, and good mechanical and abrasion resistance.11,99101 Low and ultra-low cement castables
usually require 37% water for placement, depending
on the grade.14,33,99
To appreciate fully modern refractory castables the
inter relation between particle packing, dispersion
technology, and rheology is critical. Understanding
the relation between the first two of these gave rise
8 Relations between particle packing, dispersion,

and rheology
to the new range of LCCs and ULCCs, while incorporating the third further improved the overall understanding of the technology and allowed the
development of SFCs (Fig. 8).
Particle packing, dispersion, and rheology
The main idea behind LCCs and ULCCs is to reduce
the water requirement for placement while maintaining strength. A major breakthrough in the development of this technology was the realisation that
this could be accomplished by improving the packing
density of the material. More ecient particle packing
reduces the maximum size of the interstices between
particles. For a size distribution which packs more
eciently, less of the liquid is segregated in large
interstices and more of it is eectively mobilised in
flow. The packing density of about 62% for a monosize system can be increased above 75% by adding a
specific proportion of a finer size that packs eciently
in the interstices among the coarse fraction.102
However, the idea of reducing the water requirement for placement by simply improving the packing
density of the castable would not have been successful
without the proper use of additives to allow adequate
dispersion of the submicrometre powders. A range of
chemical additives are used for this purpose including sodium carbonates,8,89,102 sodium silicates8,102
and
borates,102
sodium
pyrophosphates,8,102
hexametaphosphates44,60,85,103,104
and
tripolyphosphates,85,103,105,106
ammonium102,104
and
sodium102,105,106 polyacrylates, sodium sulphonates,102,106 sodium citrates38,102 and gluconates,38 and
many others oered commercially under proprietary
names such as Darvan 7S (organic polyacrylate polymer) and Castament FS10 (polyglycol based polymer).89 These deflocculants are used separately or in
combination with each being used to deflocculate a
particular type of particle, often in small amounts,

usually between 005 and 05%.
Refractory castables consist mainly of fine powders,
aggregate, and water, and it is generally agreed that
the workability of the material is governed by the
flow properties of the fine powders.107 Therefore,
the study of abnormal flow properties in a fine
powderwater system, such as slurries and pastes, is
important. Rheology is the science of flow and
deformation of materials.102,108,109 In a suspension of
completely dispersed particles, the shear resistance
depends primarily on the viscosity of the liquid and
the interparticle forces. In such a system, the eective
stress, or interparticle stress, is independent of pressure imposed in processing. However, in a more
crowded slurry, as is the case with castables, shear
may be momentarily blocked by neighbouring
particles. The resistance to shear flow is dependent
on particle translation away from the plane of shear,
which is time dependent. The shear resistance will be
very shear rate dependent. It also depends on mechanical interactions between particles. In a nearly closepacked system, initial flow produces significant contact stress between particles. Volume dilation of the
system must occur to accommodate shear flow. In
these systems the eective stress and the shear resistance is not independent of the confining pressure.102
In castables, the situation is further complicated by
the presence of aggregates, whose elastic and plastic
characteristics, and importantly segregation tendency,
play an important role in the flow properties of the
material.109 Studart et al.110 obtained a rheological
map by considering viscosity, yield stress, and
absorbed energy to obtain cement free, self-flowing
(see Non-cement or cement free castables and Free
or self-flowing castables below) HACs. Both particle
size distribution and matrix rheology are important
when manufacturing such castables.
Refractory castables are subjected to a wide range
of shear rates during processing and installation,
varying from the very low rates required for gravity
levelling (101 s1) to the very high shear rates
characteristic of spraying (105 s1), through the intermediate rates usually used in pumping and mixing
operations (1103 s1). Above a particular shear rate,
the hindered rotation and particle interference may
cause the appearance of shear thickening or dilatant
behaviour. Low cement castables characterised by
dilatant behaviour are subjected to high resistance to
flow at high shear rates during the mixing process,
and therefore proper mixing is only possible with
excess water, which is undesirable. The absence of
shear thickening is also important in the pumping of
castables. Increasing the solids loading (solid concentration) in the system generally decreases the shear
rate at which dilatant behaviour begins. Dilatancy
may be reduced by the use of fine particles, such as
microsilica, or any ultrafine material exhibiting significant pseudoplastic behaviour at high shear rate,
including ultrafine alumina (<05 mm). Dispersion of
agglomerates, by the use of deflocculants, or modification of the particle size distribution to produce
additional fines may also extend the range of shear
rate before shear thickening is observed in the castable. As for the fines, it is generally believed that a
narrower particle size distribution increases dilatant

behaviour. Finally, it has been shown that particles
of a more irregular shape not only cause an increase
in viscosity but also a severe dilatant behaviour,109
which is understandable since anisometric particles
produce a larger eective hydrodynamic volume
during flow.102
Submicrometre (superfine) matrix additions
According to the French patents,46,47 the main role
of the submicrometre powder additions is to act as a
filler, exactly filling the void spaces between the larger
particles, so that the densest possible packing is
achieved. Therefore, any refractory material could be
used, as long as it was solid and did not react with
water.110 Submicrometre powders commonly used in
the early years of this technology included alumina,
silica, chromium oxide, zirconia, titanium oxide, silicon carbide, clay minerals, and even carbon.14,33 From
these, two relatively new refractory raw materials
have come into significant use in both LCCs and
ULCCs: superfine silica powder and reactive alumina.
Colloidal silica
Silica fume, also referred to as fumed silica, volatilised
silica,79 silica flour, or white carbon,8 is a byproduct
of silicon metal production, with the quality variations
inherent to any byproduct. Only in the last two
decades has this material been supplied at a consistent
quality level. Many of the early field problems with
LCCs, such as erratic setting behaviour and low
strength, are directly traceable to variable quality
silica fume. The materials purity and pH have been
shown to have drastic eects on LCCs, with impurities, such as iron oxide and alkalis, reducing the
strength and increasing the viscosity, respectively, and
a lower pH increasing the setting time.14,111
The term microsilica was later introduced by Elkem
A/S for the material obtained after cleaning, classifying, and homogenising the silica rich fume released
during production of ferrosilicon and silicon metal in
electric arc furnaces.79,112 Microsilica is an amorphous
silicon dioxide consisting of submicrometre spherical
primary particles with an average diameter of
~015 mm. These spheres are the building units of
primary agglomerates which consist of a few spheres
bonded together by material bridges. Thus, the eective size distribution becomes rather wide in the
submicrometre range. This wide particle size distribution is believed to bring beneficial eects, as it
increases the packing eciency and enhances the
workability of the concrete.112
High purity microsilica from the production of
metallic silicon is usually preferred for refractories
applications.43,44 In refractory castables, use of high
quality, high purity microsilica is almost mandatory,
since low purity microsilica reduces flow and increases
water requirement for placement.113 The material is
highly reactive in cementitious and ceramic bond
systems, leading to improved ceramic bonding (forming, e.g. mullite and forsterite) at reduced firing temperatures both in high alumina and magnesia
based products. Microsilica is usually available in
undensified (U) and densified (D) forms. Undensified
microsilica has a relatively low bulk density

(02045 g cm3) and is readily dispersed in refractory concretes improving casting properties. Densified
microsilica contains loosely bonded secondary
agglomerates which increase the bulk density
(0506 g cm3) and improve the handling characteristics of the material, but it requires a high intensity
wet mixing to assure complete dispersion. There is
no dierence in chemical composition between
undensified and densified microsilica, provided the
grade is the same. The main physical and chemical
properties of microsilicas commonly used in refractories applications are listed in Table 10.
The primary function of microsilica in refractory
castables is to act as a filler. Once properly dispersed,
microsilica fills the voids between the coarser particles,
releasing the entrapped water and increasing the
packing density. In this sense, microsilica has traditionally been found to be more eective than fine
calcined aluminas, though this situation appears to
be changing as new much finer superground reactive
and dispersing aluminas become available.114,115 It is
claimed that use of microsilica reduces the open
porosity from about 2030% to 816% after firing
at 1000C, and that this reduces the characteristic
drop in strength at intermediate temperatures often
observed in conventional castables.116,117
However, acting as a filler is by no means the only
eect of microsilica in refractory castables. Studies
with microsilica containing cement pastes have shown
that microsilica reacts with the calcium aluminate
phases in the cement and water to form zeolithic
CASH phases.116 This complex pseudozeolithic bond,
just like the zeolites themselves, is characterised by a
weak water binding potential and, consequently, the
chemically bonded water is not released abruptly in
a narrow temperature interval, but rather progressively over a wider temperature range. Because of this,
it has been argued that castables with a pseudozeolithic bond are not prone to explosive spalling during
drying out.117 However, the mechanism by which
microsilica reacts with CACs is not yet fully
understood.8
In microsilica containing castables, the physical
and chemical characteristics of microsilica can drastiTable 10 Typical properties of microsilica
Mineral
Typical chemical composition,
wt-%
SiO
2
Al O
2 3
CaO
MgO
Fe O
2 3
Na O
2
KO
2
PO
2 5
SO
3
C
Loss on ignition (750C)
Median particle size, mm
Surface area, m2 g1
pH
Bulk density, g cm3
Undensified
Densified
9700
040
015
030
010
010
020
...
...
...
...
015
1828
68
...
...
960
971
983
9600
040
020
030
010
010
040
010
010
180
200
...
22
65
9750
040
020
010
010
010
030
010
010
050
060
...
20
60
9830
020
020
007
005
004
025
006
001
040
060
...
...
53
025
060
040
055
040
...
cally change the properties of the system. Because of

its high specific surface area (20 m2 g1), microsilica
in some cases makes up more than 50% of the total
particle surface area of the system, and its surface
characteristics and impurity content significantly
aect the casting and setting properties of the castable.
When microsilica is added to a refractory containing CAC, this causes modifications to the original
cementitious bond phase. First, it has been shown
that hydration of cement is hindered or diluted by
microsilica, and therefore full conversion does not
occur.59,79 Second, it has also been suggested that
microsilica delays the setting of the castable by sequestering the multivalent cations Ca2+ and Al3+. Esanu
et al.118 demonstrated that fumed silica participates
actively in hydration by interacting with additive
containing water and releasing silicic acid.
Additionally, the reactive silica may react with C AH
2
8
at slightly elevated temperatures (4060C) to form
C ASH (see the section Hydration above). When
2
8
heated above 210C, the chemically bonded water is
released, and C ASH dehydrates and becomes
2
8
amorphous. From ~1000C upwards silicate liquid
may form and gehlenite (C AS) and anorthite (CAS )
2
2
crystallise.118,119 At these temperatures and up to
~1200C, microsilica containing castables exhibit
superior properties compared with microsilica free
castables, including a reduction in porosity of about
58% and a large increase in cold crushing strength,
presumably due to the high reactivity of microsilica.117
However, as the temperature is further increased
above 1200C, the hot strength deteriorates,
depending on the amounts of cement and microsilica,
due to eutectic liquid formation in the CAS ternary.
However, it has been observed that, in high alumina,
microsilica containing LCCs and ULCCs, the hot
strength sometimes increases significantly above
1300C, reaching its maximum around 1400C, only
to drop again at 1500C.44 The increase in hot
strength is believed to be caused by the growth of
elongated needle-shaped mullite crystals from the
liquid phase, which interlock the structure improving
the bond. As soon as the castable is heated to 1400C,
the bond phase of the castable reacts and produces a
viscous liquid formed mainly from cement and microsilica. Within a few hours, the liquid starts to dissolve
alumina, which goes into solution with silica and
lime; the liquid becomes saturated, and mullite precipitates. As mullite is formed, the composition of the
liquid changes, and its amount decreases. The final
compositions of the glassy phase are either close to
anorthite or comparatively richer in silica. Further
mullite precipitation is hindered, either by long
diusion paths or because the glassy phase reaches a
stable composition.44,119
Studies involving addition of microsilica to high
alumina LCCs and ULCCs indicate that there is a
minimum amount of microsilica required for mullite
precipitation, which depends on the amount of
cement. It has been suggested that for castables with
15% cement (027%CaO), strengthening due to the
formation of mullite is only observed for microsilica
contents above 6%. For castables with 75% cement,
at least 10% microsilica is necessary, but since there
is always some liquid present in the castable, and this
increases with the cement content, the high cement

castables usually show lower hot strength.120 The
subsequent drop in strength observed at 1500C,
despite the precipitation of mullite, was attributed to
the presence of impurities, particularly alkalis from
the alumina, and further studies were carried out to
confirm that reducing the alkalis in the system could
improve the strength.44 However, despite the overall
improvement in hot strength, both at 1400 and
1500C, this did not change the general trend, since
the strength also dropped at 1500C for the low alkali
compositions.
Based on a series of studies on the use of microsilica
in high alumina LCCs and ULCCs,44,117,119,120 it was
suggested that to increase the castables hot strength
both the impurities and the cement content should
be lowered to a minimum, while the amount of
microsilica should be increased.119 While this is true
to a certain extent, since increasing the amount of
silica with respect to that of the cement actually
pushes the composition of the matrix towards the
silica corner in the CAS alkalis quaternary system,
and therefore away from any eutectic liquid in the
system, it could be argued that this could also be
achieved by reducing the amount of microsilica with
respect to that of the cement. Of course, this would
also require improvements in the properties of the
castables at the lower temperature range, where the
addition of microsilica boosts the strength and
reduces the porosity. This, fortunately, has been made
possible by the use of special superground reactive
aluminas, which improve packing and speed up the
development of a ceramic bonding phase at much
lower temperatures (see the section Calcined alumina
below).114,115
The benefits of adding microsilica to bauxite based
LCCs and ULCCs are clear since these materials
already contain silica and therefore the eutectics in
the ternary CAS system cannot be avoided, other
than by reducing the amount of cement.43,121
However, as far as high alumina, LCCs and ULCCs
are concerned, the use of microsilica, despite its
acknowledged beneficial eects to the rheology and
packing of the system, is detrimental to the hot
strength at temperatures around and above 1500C,
due to the formation of liquid phase. One advocated
solution to this problem is the reduction in the
amount of cement, in some cases down to levels as
low as 05%. But so far this has only proven feasible
with the simultaneous addition of cement (05%) and
hydraulic alumina (05%), so that both the setting
time and flow could be properly adjusted.33,52 In this
case, the bond is predominantly interlinked mullite
needles, and it has been shown that for higher contents
of microsilica (10%) the drop in hot strength at
1500C may be significantly minimised, and the hot
modulus of rupture in some cases approaches that of
microsilica free HACs.122 However, though this issue
has not yet been properly addressed, the mullite bond,
as it is in bricks, is often more prone to corrosion by
metal and steelmaking slags than the high alumina
bond. Therefore, for applications where corrosion
resistance is the ultimate goal, such high microsilica
ULCCs are not appropriate.
Calcined alumina
Calcined aluminas can be divided into three main
categories based on both sodium oxide content and
total impurities.123 The first category includes normal
calcined alumina with a soda content greater than
01%, usually between 018 and 055%, and
~990995%Al O . The second category contains
2 3
calcined aluminas, sometimes referred to as low soda,
with an alumina content of about 997% and less
than 01% soda. The third category includes high
purity calcined aluminas with at least 999%Al O .
2 3
Almost all calcined aluminas, including those for
refractory applications, are produced by heat treatment of gibbsite from the Bayer process.
After calcined alumina aggregates are produced,
they can be further processed, by milling to separate
them into their individual crystals. The time and
intensity of this step determines the particle size
distribution of the finished product. Normal calcined
aluminas, also called milled aluminas,101 are usually
ground below 44 mm (9599%), but these agglomerated aluminas have not been completely separated
into their ultimate crystals. In applications where a
more completely ground alumina is required, the
superground aluminas, also referred to as thermally
reactive aluminas, or simply reactive aluminas, should
be used. These are finely ground calcined aluminas
whose relatively high surface area fine crystals exhibit
higher densification and reaction rates when compacted and sintered into ceramic products. Sintering
temperatures required to densify completely ceramics
made from fine superground aluminas are usually
200C lower than those made from regular ground,
coarser aluminas. These reactive aluminas are not,
however, capable of hydraulic activity to form chemical bonds at ambient temperatures. Hydratable aluminas (such as r-aluminas) which are capable of forming
room temperature chemical bonds in cement free
castables are considered in the section Non-cement
or cement free castables below.
In refractory applications, both normal and low
soda aluminas are mainly used. Normal soda aluminas have traditionally been recommended for alumina enrichment of refractories where a small amount
of soda can be tolerated.101 However, in modern
castables technology, not only has the soda content
of the aluminas come under closer scrutiny, because
it can greatly aect the dispersion of alumina, increasing the viscosity,111 and the hydration of cement,
shortening the induction period,74 but also the physical characteristics such as crystal shape and size,
particle size distribution, specific surface area, a-Al O
2 3
content, compacting behaviour, and sintering reactivity. The particle size distribution of the alumina plays
an important role in filling the interstices between the
larger aggregates to increase packing density, and it
has been found that combining several kinds of
ultrafine alumina with dierent particle size distributions may further contribute to reduce the water
requirement for placement.23 The use of calcined
aluminas with multimodal particle size distributions
may have similar eects on packing.114 In general,
the finer the alumina the greater its reactivity, which
improves sintering at lower temperatures speeding up
early development of a ceramic bond. Usually, as the
crystal size increases, green density increases. Also, as

the crystal size distribution is broadened, green density increases. High green density minimises shrinkage
during sintering. Coarser crystalline aluminas exhibit
minimum shrinkage at 1500C, while finer aluminas
are in the final stages of sintering at this temperature.
In low moisture LCCs fine aluminas that exhibit high
reactivity but low water demand are particularly
useful. These are usually low soda aluminas that
exhibit high green densities.123
A range of calcined aluminas are available, including the most recent type referred to as dispersing
aluminas. These are characterised by a bimodal
particle size distribution, which improves packing,
and are believed to contain organic ingredients that
allow better dispersion and control of the cement
setting.114,115 Some of the most commonly cited commercial calcined aluminas101,123 are listed in Table 11
which gives their main properties and characteristics.
The use of fine reactive aluminas results in LCCs
with excellent hot properties and very low mixing
water requirements for placement. Unfortunately,
SFCs formulated without microsilica can become
dilatant, making them unsuitable for pumping.114
Aggregates
Low and ultra-low cement castables are basically a
mix of two main components: the refractory aggregate
and the binding system.106 The fine fraction below
45 mm usually represents the bond system, which
consists of the hydraulic binder, fine and superfine
ceramic powders, and admixtures of deflocculants,
water reducing agents, set retarders, and accelerators.
This fraction will become the matrix of the solid
concrete after setting and will give rise to a ceramic
bonding phase on firing, which will bind together the
refractory aggregates (see Fig. 1). Owing to its multiple roles in controlling the flow behaviour and
setting time of the castable, as well as the strength
and properties of the binding ceramic matrix, the fine
portion of these materials has been widely investigated. However, the refractory aggregate, which is the
fraction above 45 mm, is also extremely important in
this partnership, not only with respect to the particle
size distribution of the mix, but also regarding the
overall chemical composition of the material. The
aggregate system normally comprises 6085% of the
castable mix, and its chemical composition and physical characteristics significantly aect the final properties of the castable, particularly thermal shock and
corrosion resistance.
Practically any natural or synthetic refractory oxide
that is normally used for refractory bricks can be
used as aggregate in LCCs and ULCCs. However,
alumina, fused or sintered, is the most common
aggregate used due to its high strength, relatively low
thermal expansion coecient, and good resistance to
chemical attack, though it may be dissolved at high
temperatures in molten alkalis and calcium containing
silicates. Besides, in CA cement systems, alumina is a
compatible oxide, which does not change the refractoriness of the binary CaOAl O system (Fig. 2),
2 3
and this also accounts for its widespread use in
cement containing castables.

Table 11 Typical properties of reactive calcined aluminas43,115
Type of alumina
16SG
Composition, wt-%
Al O 43,115
2 3
SiO
2
Fe O
2 3
Na O
2
Crystal size, mm
Particle size, mm
Surface Area, m2 g1
Green density, g cm3
Fired density, g cm3
Compaction pressure, MPa
Sintering
Temperature, C
Time, h
152SG
A17
1000SG
3000FL
RA7
RA10
RA15
...
...
...
...
...
...
...
...
997
003
001
008
997
004
004
008
997
003
001
008
997
002
002
008
997
002
002
008
...
...
...
...
04
05
10
215
391
345
15
15
3
225
384
345
325
30
3
250
375
345
04
05
10
215
391
345
325
30
3
250
375
345
...
1540
1
1620
1
1750
1
White fused alumina (WFA) is produced by fusion

of calcined alumina in an electric arc resistance furnace, and its microstructure is usually characterised
by the presence of sharp and fractured corundum
grains. The main impurities present in white fused
aluminas are sodium and potassium, usually as
a-alumina, iron oxide, titanium oxide, and calcium
oxide. Brown fused alumina (BFA) is produced by
fusion of bauxite, and its main impurities are iron
and titanium oxides, in amounts often greater than
those found in white fused alumina.
Sintered aluminas are also prepared from calcined
alumina produced by the Bayer process, so soda
exists in small amounts as the major impurity.
Sintered aluminas having flat table-like a-Al O crys2 3
tals, usually averaging 50 mm or greater, are termed
tabular alumina (TA). Because of the grain boundary
porosity entrapped during rapid sintering, tabular
alumina has a particle bulk density in the range
340365 g cm3, with characteristic closed spherical
porosity typical of a fully sintered ceramic with secondary recrystallisation. The excellent thermal shock
characteristic of tabular alumina is attributed in part
to the closed spherical pores, which apparently act as
crack arresters. Open porosity is characteristically
low (<5%).99
Microstructural evolution on drying and firing
Low and ultra-low cement castables are carefully
graded for maximum packing density. Besides their
characteristic low cement content, they contain superfine or colloidal particles, such as silica fume and
alumina, deflocculants, and setting control additives,
that help to reduce further the water requirement for
placement and improve the ceramic bond. The compositions of some LCCs and ULCCs are given in
Table 12.
During drying (dehydration) all of the reactions
described in the sections Dehydration and firing and
Microstructural development above, occur in the
presence of aggregate phases and various additives
made to aid installation. A significant characteristic
of LCCs and ULCCs is the very low water addition
required for mixing and placement, which accounts
for the low porosity of the cast structure and improves
the strength (see the section Particle packing, disperInternational Materials Reviews 2001 Vol. 46 No. 3
1540
1
1750
1
...
11
3
...
...
21
22
...
350
27
37
...
340
360
...
...
...
1650
...
1650
...
1650
...
sion, and rheology above). This dense microstructure,

which accounts for the superior qualities of these
materials, also poses the biggest challenge. Drying
and baking out of LCCs and ULCCs is often dicult,
particularly in thick installations, because of the low
gas permeability caused by the low porosity of these
materials.8,14,33,37 Major problems are the occurrence
of cracks and the risk of explosive spalling,103 believed
to be due to the internal vapour pressure, which
builds up within the cast structure, and whose magnitude ultimately exceeds the material strength.8 It is
also believed that the internal vapour pressure
depends largely on the curing temperature and material properties, such as the strength and permeability.
Balancing between the vapour pressure and the
strength undoubtedly determines whether an
explosion will occur or not during the drying stage.
But for this, it is essential to improve the permeability
of these highly dense materials, preferably without
compromising the strength. Organic bake out fibres
are used to reduce the possibility of explosive spalling
and they usually allow increased heating
rates.14,47,99,124 They have their origins in a patent by
Hoganas in 1974, but refinement of this technology
to make use of small polypropylene fibres occurred
only in the 1980s.14 This technology is based on the
addition of small amounts (not more than 05% and
usually between 005 and 02%) of organic fibres
which shrink and melt during the early stages of
castable bake out, thus increasing the permeability
and creating channels for water removal during the
critical dehydration period, and enabling stress
release.
Stainless steel fibres are also believed to increase
the spalling resistance of castables at high temperature, preventing catastrophic failure of the installation. They are usually added in amounts varying
between 1 and 4% by weight. Their function is to
hold the castable together when cracking occurs, thus
increasing service life.14
Metal powders, such as aluminium, have also been
widely used to increase castable resistance to explosive
spalling. The release of H during the reaction of the
2
metal with water is believed to generate gas pipes in
the dense castable structure, thus increasing the permeability.99 It has also been suggested that the heat

Table 12 Composition (wt-%) of low and ultra-low cement castables
Ref.
44
105
105
101
80
104
83
83
83
Spinel
Fused alumina
Tabular alumina
Calcined bauxite
Kyanite
Microsilica
Calcined alumina
Reactive alumina
Dispersing alumina
Hydraulic alumina
CA cement
SHMP
Polyacrylate (Darvan)
Polyglycol (Castament)
Sodium carbonate
Citric acid
Water, wt-%
...
...
...
825
...
6
...
10
...
...
13
018
...
...
...
...
5
...
...
...
680
10
6
...
10
...
...
6
020
...
...
...
...
5
...
715
...
...
...
10
...
17
...
...
15
...
005
...
...
...
4
...
840
...
...
...
8
7
...
...
05
05
...
005
...
...
...
41
...
710
...
...
...
5
95
85
...
...
6
...
005
...
...
005
41
...
...
78
...
...
...
...
17
1
...
5
...
...
...
...
...
40
...
...
80
...
...
5
...
10
...
...
5
...
005
...
0005
0015
50
...
...
80
...
...
...
...
15
...
...
5
...
...
05
005
015
50
23
...
60
...
...
...
...
11
...
...
6
...
...
005
0005
0012
50
released during the exothermic reaction of aluminium

with water is eective in decreasing the setting time
and strengthening the material.103 An additional
problem is control of the CAC reaction which changes
the pH as the CAC goes into solution, eecting the
aluminium reaction, setting, and hydrogen generation.
Whatever the case, this technique requires that precautions be taken to vent the H properly to prevent
2
formation of explosive atmospheres.
In general, on firing LCCs and ULCCs the reactions described for pure CAC (see the section
Dehydration and firing above) and for conventional
castables (see the section Microstructural development above) occur. However, the matrix system in
LCCs and ULCCs contain additional fine additions
of silica and alumina (see the sections Colloidal silica
and Calcined alumina above) which will react with
the lower CA cement content present compared with
a conventional castable. The CAS and CMAS
phase diagrams indicate the phases expected at equilibrium for the local matrix composition.125,126 If the
bond does not include fine silica low cement, compositions are in the alumina phase field while at the high
cement levels of a conventional castable the matrix
quickly moves into the CA region. As silica is added
6
(in LCCs and ULCCs) the matrix moves back to the
alumina field remaining there even with up to 20%
silica. Matrix compositions are designed to avoid the
low melting compositions (anorthite and gehlenite)
accomplished by minimising the matrix silica at high
cement levels or limiting the matrix CaO to <8% in
silica containing LCCs and ULCCs.125
Aggregate phases may have a significant eect on
microstructural evolution at high temperature (above
1000C). Sarpoolaky et al.127 examined LCCs with
dierent aggregates (TA, WFA, BFA, and spinel) but
a similar CAC/fine alumina bond. On firing at 1000C
the bond was similar in all four samples consisting
predominantly of alumina, CA, and CA . However,
2
after firing at 1600C platey CA and alumina was
6
present in the bonds of the TA, WFA, and spinel
grain samples but the BFA sample bond contained
calcium titanates, more rounded CA , and evidence
6
of a large volume of liquid being formed leading to
increased density. This had important eects on the
corrosion mechanisms in these refractories.
Properties
The main technical advantages of LCCs and ULCCs
are their excellent physical properties, such as high
density, low porosity, high cold and hot strengths,
and high abrasion and corrosion resistance.14,33 The
porosity and mechanical strength of refractory castables vary with the temperature. A conventional
castable has an open porosity of about 917% after
drying and ~2030% after heat treatment at 1000C.
Most LCCs have an open porosity not higher than
10% and 16% after drying and firing, respectively.
Low cement castables usually possess a much finer
pore size distribution than conventional high cement
castables, which further contributes to increase the
corrosion resistance, by hindering the penetration of
metals and slags.30 The cold strength of LCCs rises
steadily with temperature and is often higher than
that of a conventional castable of similar composition
at all temperatures after dehydration.33 Low cement
castables usually have higher modulus of rupture and
lower creep values than conventional high cement
castables.8 All these characteristics provide superior
performance over conventional high cement castables
and other monolithic materials, such as ramming
mixes, plastics, and gunning refractories. However,
high cement castables are more robust with regard
to installation procedures and ease of placement,37,40
while LCCs and ULCCs, are more sensitive to installation parameters and variations in water addition
and casting conditions, such as the ambient temperature, may aect pot life, hardening time, and curing
strength.8,37,40
Recent developments
Non-cement or cement free castables
Cement free castables are used in numerous molten
iron and steel contact applications, where the elimination of lime in the refractory matrix increases use
temperature. They usually do not possess the superior
physical and mechanical properties of LCCs and
ULCCs, but do possess better corrosion resistance to
metals and slags.14 Cement free castables use a variety
of bonding systems, including clay minerals, silica gels,
hydratable aluminas, and phosphates.37,51,52,128130
Among the dierent binding systems for noncement castables, hydratable aluminas have attracted
great attention. The first reported applications came
from Japan in the early 1980s.37 Hydratable aluminas
are amorphous mesophase transition aluminas (e.g.
c, r, x), which, similar to cement, harden hydraulically.
They are produced by the rapid dehydration of
gibbsite (Al(OH) ). When in contact with water,
3
c-alumina rehydrates, forming pseudoboehmite
(AH ) and bayerite (AH ). During heating, the
12
3
hydrated phases lose their chemically bound water,
giving rise to the stable form of alumina (a-Al O ),
2 3
which at higher temperatures will help to develop a
strong ceramic bond.37,128 The hardening reaction of
the transition alumina can be accelerated by the
inclusion of alkali metal salts or delayed by the use
of carboxylic acids.128
When used as a substitute for the cement, transition
aluminas are usually combined with microsilica to
promote the formation of mullite at high temperatures
and improve hot strength.37,51,52 However, it has been
found that small additions of CAC may still be
necessary, usually around 05%, to control the setting
time of the castable.51,52 This is because a castable
with a low hydraulic alumina content will not set,
and if more hydraulic alumina is added to make it
set, good flow is only possible with an excess of water,
which increases the porosity.
Like all binding systems, hydratable aluminas also
have their own problems and disadvantages,37,128
such as the high risk of explosive spalling at low
temperatures, usually around 200300C, because of
the impervious structure. Besides, curing of a-alumina
containing, cement free castables must commence at
temperatures above 18C, or strength is not fully
developed. Finally, they are expensive.
Free or self-flowing castables
In many cases, castables are selected as the preferred
lining materials just because bricking may be dicult
or even impossible. Low and ultra-low cement castables are often the first technical choice, but whether
these materials can be satisfactorily installed is not
always immediately apparent. Among the many factors that aect the quality of the installation, and of
course the performance of the lining, are the following:
inecient mixing, excess water additions, dicult
placement, and inexperienced personnel.17 Flow of
LCCs and ULCCs is usually promoted by internal
or external vibration, since these materials are thixotropic in nature, but this alone is not always enough
to assure complete filling and good consolidation of
all parts of the lining.
In an attempt to overcome the problems of installation associated with the vibration placement, a new
class of high performance LCCs and ULCCs, characterised by a consistency after mixing that allows the
material to flow and degas without the application of
external energy, was developed in the mid-1980s.
These materials were termed self-flowing castables
(SFCs), and were developed by simply modifying the
rheology of the LCC and ULCC systems, mainly by
changing the shape and size distribution of the aggregates and by the judicious choice of defloccuInternational Materials Reviews 2001 Vol. 46 No. 3
lants.9,17,31,48,131 The basic idea was to reduce the

points of contact between the aggregates, which slow
the flow, by increasing the volume of the matrix, yet
keeping its density high.48 With water additions in
the range 4580%, depending on the product type,
these castables self-flow under their own weight, easily
filling intricate forms and shapes and, because of their
cohesive consistency, they can be installed without
separation of the fine material or the fluid phase from
the aggregate.
Early low cement, free flow castables had good
flow characteristics, but strengths were significantly
below those of vibrated LCCs. Other free flow versions had high cement levels, and were simply
improved flow, conventional castables. Modern selflevelling castables utilise a sizing and a cement level
similar to those of LCCs and ULCCs, but many
separate features of these products have been
optimised to generate self-flow behaviour at low water
levels. The self-flow technology can be applied to a
wide variety of compositions, ranging from fumed
silica and bauxite based products to high alumina
and silicon carbide based castables.15 However,
despite the significant improvements in the technology, it should be noted that if normal LCCs can
be easily installed at low water additions using
vibration, then their physical properties are generally
superior to those of free flow castables.17
Self-flowing refractory castables also have their
limitations, in particular, control of the setting time,
that should be long enough to allow the natural degas
of the castable and yet short enough to prevent
sedimentation or segregation.48 Other drawbacks
relate to the strong influence of temperature on flow
behaviour and setting time, with temperatures above
30C being particularly harmful and detrimental to
the installation quality;31 dierences in plant sites and
applications, which require dierent but controlled
placement and demoulding times; and dilatant flow
behaviour, which complicates handling and dosing.
Variations in the cement reactivity, which influenced
placement and setting time substantially in first generation self-flow systems, have now been addressed by
the cement producers who now supply a consistent
product. Finally, the water demand of self-levelling
systems is still considerably higher than that of
vibration castables and, as much as the thixotropic
LCCs and ULCCs, overwatering significantly aects
the mechanical strength and corrosion resistance of
these materials.115
Studart and co-workers recently outlined development of castables which are both cement free and
self-flowing achieved by close control of matrix
particle size distribution and rheology.110,132134
Shotcreting self-flowing castables
Shotcreting, wet gunning, or shotcasting, is an installation technique by which a refractory composition
is first wet mixed and then transported through pipe
or hose to the site of placement, where it is sprayed
on to the surface where it remains with no
rebound.16,135138 The Portland concrete industry has
been wet shotcreting since the early 1950s, while the
first results on wet shotcreting of refractory castables
were published in 1963.139 However, it was not until

1991 that equipment and material improvements
enabled the technique to become an eective installation tool. The refinements of the technology
stemmed largely from the increasing environmental
restrictions on dust and the desire to improve furnace
availability, while reducing the time required for
constructing form work.16,135
The development of LCCs and ULCCs with
improved flow characteristics was a major step in the
development of the technology, since it permitted the
use of pumpcasting techniques similar to those used
in the Portland cement industry, and opened the door
for the use of sprayable low cement refractories.135
Simultaneously, a concentrated eort was made by
pump manufacturers to design pumps that would
provide the necessary pressure to transport heavier,
more viscous refractory materials through the relatively small hose diameters needed for proper
mobility.16
A key feature of wet shotcreting SFCs is that wet
mixing is an independent operation, and therefore the
mixing process can be optimised for each particular
product and the necessary installation conditions
before the material is fed to the pump. Most common
mixers used in the refractories industry can be used
successfully for shotcreting, as long as the output of
wet mixed material matches the pumping rate, which
is usually between 5 and 9 t h1. The pump used
successfully on most jobs has dual reciprocating
hydraulically powered 75 mm dia. material cylinders,
whose pistons are capable of pressurising the refractory castable to above 14 MPa. The nozzle at the
discharge end of the hose is similar to most nozzles
used for dry gunning, but includes several minor
important changes. Air and a set activator, or accelerator, are introduced through enlarged injection holes,
and this breaks the material into smaller particles
and mixes it with the accelerator, while providing the
energy for the spraying action as the material exits
the nozzle and is projected on to the surface to be
covered.16,135 The reaction of the set activator with
the low moisture castable stiens the material on the
wall, allowing close control of lining thickness.
Most self-flow shotcreting mixes are based on low
moisture, low cement dense castables and conventional lightweight products, though the technique is
becoming more attractive to non-cement systems.
However, regardless of the binding system, any selfflowing mix used for wet shotcreting must have
particular characteristics. First, the top-size aggregate
must be properly chosen to prevent nozzle plugging
and reduce rebound. Second, the SFC must show
minimum dilatancy, good cohesiveness, and low tendency to segregation. Besides, after experiencing pressures and movements over significant distances during
pumping, the material must remain fluid enough to
break up inside the nozzle so that the spraying action
is eective. Finally, the set activator, or accelerator,
must fully penetrate and activate the castable to
provide sucient and rapid stiening when the material is sprayed on the walls.
The accelerator is actually a liquid system containing a soluble set activator. Ideally, it should be
environmentally friendly, free of particles to prevent

clogging of the needle valve, and of low viscosity, so
that it can be easily mixed with the castable.
Chemically, the accelerator must thicken or stien
the material quickly. However, it is important that
the material remains in a plastic state for a reasonable
length of time to allow trimming and finishing of the
covered area. Accelerators or set activators that cause
rapid setting or hardening of the castable are not
acceptable, because they lead to laminations and
usually clog up the nozzle.16 Accelerators used in
SFCs include aluminium sulphate,137 polyaluminium
silicate sulphate (PASS),137 sodium silicates,137 and
alkali or alkaline earth carbonates, silicates, and
nitrates.16
Spinel and magnesia based castables
The increasing importance of steel ladles in modern
steelmaking technology, and the ever increasing concern with steel cleanliness and the eciency of steel
desulphurisation achieved in secondary steelmaking,
has led to the development of aluminaspinel and
aluminamagnesia castable compositions. First,
aluminaspinel materials, made up of a mixture of
WFA or tabular alumina and MgAl O spinel aggre2 4
gates, superseded high alumina castables, due to their
better corrosion resistance, and became widely used
to line the walls, bottom, and impact pad of ladles.21,24
However, these castables were still susceptible to some
structural spalling, as the slag-penetrated layer tended
to peel o in service.24 Recently, self-forming, or in
situ aluminamagnesia spinel castables became available made up of mixtures of aggregates and fine
reactive magnesia and alumina powders. Reaction of
the fine fractions leads to in situ matrix spinel
formation.
Reactive magnesias include dead burned, sea water
derived MgO or lightly calcined Mg(OH) . Reactive
2
MgOs hydrate to brucite (Mg(OH) ) exothermically
2
evolving large amounts of heat and with an associated
22 vol.-% expansion which may lead to explosive
spalling during installation so that too fine a MgO
powder cannot be used. Alternatively, the MgO can
be coated to prevent early uncontrolled hydration.140
Use of already hydrated brucite as the starting material
overcomes this problem141 and provides a reactive
MgO on firing which readily reacts to form spinel.
Bier et al.140,142 examined the significant influence of
fine MgO on the rheology and hydration of CAC
based castables. The presence of magnesia reduces
both the fluidity and working time of magnesia containing CAC based castables, with the fineness of the
magnesia powder being particularly important.142 The
use of admixture combinations are necessary to master
the rheological properties of these castables, and they
usually consist of deflocculants, such as polyacrylates
(Darvan) and sodium phosphates, and set retarders,
such as citric acid and Na CO .85,115,142 Hydration of
2
3
hydratable aluminareactive MgO mixtures also leads
to large heat evolution via formation of hydrotalcite
type phases (Mg Al CO (OH) .4H O).82 A deleteri6 2
3
16
2
ous volume increase is also associated with hydrotalcite
formation.
match for the magnesiacarbon bricks, usually used

as the standard lining in the slag zone of ladles.22,147
Conventional basic castables are mostly used for
repairs, and are rarely considered as premium quality
products, because of their poor physical and thermomechanical properties, and hydration tendency. It has
been suggested147 that the hydraulic CAC bond is
not suitable for magnesia based materials, and that a
new bonding system is necessary. Recently, a cement
free bonding system for basic castables has been
reported using amorphous silica gel bonds derived
from fumed silica.147 At high temperature, reaction of
the silica with MgO leads to development of a forsterite (M S) bond.148
2
9 Dark spinel shells on alumina particles in matrix
of ULCC146
A significant volume expansion occurs when very

fine powders react to form spinel which is greater
than the 245% predicted from molar volumes.143 The
volume expansion from direct spinel formation
together with the calcium aluminates (CA at high
6
temperature) and alumina provides a dense matrix
system.20,21,24 However, this depends on several factors, such as the amounts and particle size distributions of the powders, the presence of impurities,
and the amount of liquid phase formed at high
temperatures.24,144 If these are not properly controlled, the volume change associated with spinel
formation may cause an overall bulk volume expansion of the lining, rather than a densification of the
microstructure. Fuhrer et al.98 determined that spinel
formation occurs between 1200 and 1400C with a
tuber-like morphology interlinked with CMAS phases
and CA platelets derived from the CAC. In these
6
CMAS systems, the presence of silica is detrimental
to the refractoriness145 but it has been found that, if
added in small amounts, microsilica accelerates the
spinel formation.24 It has also been shown that silica
contributes to improving the thermomechanical properties of the castable, increasing its resistance to crack
propagation.21 Finally, it has been reported that
microsilica helps to prevent the hydration of magnesia
(acting as an anti-slaking agent), therefore improving
the service life of the castable.26,142 The matrix microstructure of a commercial in situ spinel ULCC reveals
several morphologies of in situ spinel on firing. At
1200C spinel formed in the matrix by reaction of
fine fractions while at higher temperature coarser
particles reacted to give, for example, spinel shells on
alumina grain (Fig. 9).146
Although the literature on aluminaspinel castables
is not as extensive as that on high alumina castables,
the technology of these spinel containing materials is
well established, since most basic principles of the
rheology of high alumina castables can be directly
applied to them. On the other hand, there is a lack
of understanding of the in situ spinel materials, and
this is even more conspicuous in the case of magnesia
castables. Despite the outstanding performance of
modern refractory castables, these materials are no
Future developments
Oxide based refractory castables are used extensively
in refractories applications such as blast furnaces,
torpedo ladles, tundishes, and cement rotary kilns.
However, the current Al O based castables suer,
2 3
for example, from poor corrosion and spalling resistance especially in a basic slag environment.
Unfortunately, the newly developed basic (MgO and
MgOCaO) castables also have poor spalling and
slag penetration resistance.120 One way to overcome
these problems is to introduce carbon (as graphite
flakes) to current oxide castable systems because of
its non-wettability by molten metals and slags and
high thermal conductivity. However, this causes new
problems. First, because graphite is not wetted by
water, adding even a small amount (5%) requires
also adding considerable amounts of water (>18%)
to obtain reasonable flow behaviour. This results in
high levels of porosity and lower mechanical strength
and corrosion resistance which counteracts the merits
of graphite addition. Second, problems associated
with high porosity, such as graphite oxidation and
low mechanical strength, become more serious than
in denser, pressed carbon containing bricks so that
more eective additives (antioxidants) are needed.
Although aluminium and its alloys are very eective
antioxidants and most commonly used in carbon
containing bricks, they cannot be used directly in
castable systems because of their hydration tendency.
A major research eort is underway to solve these
problems and develop carbon containing castables.149
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Castable refractory concretes

W. E. Lee, W. Vieira, S. Zhang, K. Ghanbari Ahari, H. Sarpoolaky, and C. Parr

Castable refractories containing calcium aluminate

2001 IoM Communications Ltd and ASM International.

brown fused alumina

calcined bauxite, and sintered MgO while bonding

International Materials Reviews 2001 Vol. 46 No. 3 145

146 Lee et al. Castable refractory concretes

trowelling, or projection (spraying or shotcreting).

based systems are reviewed. Finally, the possibility of

Lee et al. Castable refractory concretes 147

teristics of shotcreted LCCs were first published in

148 Lee et al. Castable refractory concretes

nature, rheological behaviour,

Calcium aluminate cements

Calcium aluminate cements

Chemical analysis, wt-%

Table 2 Classification and properties of calcium

Chemical analysis, wt-%

International Materials Reviews 2001 Vol. 46 No. 3

calcined alumina is often the choice for the high

Lee et al. Castable refractory concretes 149

highest strength among the phases listed during the

2 Binary CaOAl O phase diagram; in wt-%

The two most critical areas of cement production

Table 3 Chemical composition (wt-%) of commercial alumina cements

International Materials Reviews 2001 Vol. 46 No. 3

150 Lee et al. Castable refractory concretes

3 Reaction schemes for a CA, b CA , and c C A

CAH can be detected after 624 h. The presence of

Table 5 Properties of CAC mineral constituents

International Materials Reviews 2001 Vol. 46 No. 3

Lee et al. Castable refractory concretes 151

5 Temperature dependence of calcium aluminate

ing solution chemistry,6870 X-ray diraction,71,72

of the cement increases rapidly. The evolution of heat

As the temperature rises above 21C, the metastable

152 Lee et al. Castable refractory concretes

a 18 h, C AH hexagonal plates; b 11 d, C AH deltoid icositetrahedra

6 Hydrate microstructure in CAC with water/

stable hydrates (AH and C AH ) at higher curing

International Materials Reviews 2001 Vol. 46 No. 3

Lee et al. Castable refractory concretes 153

allowed to form during low temperature curing, the

154 Lee et al. Castable refractory concretes

a 900C; b 1200C; c, d, e 1300C; f 1400C

7 Microstructural evolution on firing conventional castable matrix96

place, and then destroyed by the dehydration process.

varies from 22 to 26%, depending on the type of

Table 9 Mineralogical changes of dehydrated high alumina cement on heating

International Materials Reviews 2001 Vol. 46 No. 3

Lee et al. Castable refractory concretes 155

has not yet allowed the development of a ceramic

Low cement castables and ultra-low

156 Lee et al. Castable refractory concretes

8 Relations between particle packing, dispersion,

particular type of particle, often in small amounts,

Lee et al. Castable refractory concretes 157

narrower particle size distribution increases dilatant

microsilica has a relatively low bulk density

International Materials Reviews 2001 Vol. 46 No. 3

158 Lee et al. Castable refractory concretes

cally change the properties of the system. Because of

increases with the cement content, the high cement