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 1 Typical powder processed refractory
refractories. The development of the low cement microstructure
systems is discussed in terms of particle packing,
dispersion, and rheology highlighting the influence
of colloidal matrix additions of silica and alumina. calcined bauxite, and sintered MgO while bonding
Recent developments including cement free, self-
systems may be based on carbon derived from pyro-
flowing, shotcreting, and basic castables are
described and the potential for carbon-containing lysed pitches and phenolic resins, mullite and glass
systems evaluated. IMR/368 from decomposed clays, or alumina and calcium
aluminate phases formed from fired hydraulic calcium
© 2001 IoM Communications Ltd and ASM International. aluminate cements (CACs). The most significant trend
Professor Lee, Dr Vieira, Dr Zhang, Dr Ahari, and Mr in refractories technology in the last two decades has
Sarpoolaky are in the Department of Engineering Materials, been the ever increasing use of monolithics, or
University of Sheffield, UK and Mr Parr is with Lafarge
Aluminates, Paris, France. unshaped refractories, which now, in many countries,
account for more than 50% of total production.
Owing to improved refractories quality their con-
sumption has decreased dramatically in the last two
Abbreviations decades while the ratio of monolithics to preshaped
refractories (bricks) has been steadily increasing.1–6
BFA brown fused alumina
The reasons for the rapid growth of monolithics,
CAC calcium aluminate cement
at the expense of bricks, are their ready availability,
CVC casting vibration castable
faster, easier, and cheaper installation, and fewer
HAC high alumina cement
corrosion-susceptible lining joints.6–11 The term
LCC low cement castable
monolithic usually includes a wide variety of material
SFC free or self-flowing castable
types and compositions, with various bonding sys-
TA tabular alumina
tems, ranging from fluid cement pastes to stiff plastic
ULCC ultra-low cement castable
WFA white fused alumina lumps.6,11,12 Monolithic materials were first used as
a distinct refractory product in 1914, when the first
Chemistry commercial refractory plastic, a simple blend of
A Al O crushed firebrick and fireclay, was produced.5,6,12
2 3
C CaO From this, monolithics have evolved into a versatile,
F Fe O widely used class of refractory materials that offer
2 3
H HO performance and cost effectiveness comparable, and
2
M MgO sometimes even superior, to those of shaped refractor-
S SiO ies. The success of monolithics is due to significant
2
T TiO advances in the type and quality of their binders,
2
aggregates, and additives as well as to innovation in
their design and installation techniques.5,6
Introduction The evolution of monolithic refractories over the
Refractories are a group of ceramic materials used in past century has been described in a recent review.13
massive quantities to line vessels in which other A significant advance in monolithics technology was
materials (such as metals, glass, and cements) are the development of refractory concretes or castables
manufactured at elevated temperatures. They consist based on CACs.6–8,11,14 Castables are complex refrac-
of large sized (up to centimetres) aggregate (filler) tory formulations, requiring high quality, precision-
phases held together with finer (sometimes submicro- sized aggregates, modifying fillers, binders, and addi-
metres), often porous, binder phases conferring the tives.11,14 Refractory castables are dry granular mater-
microstructure shown schematically in Fig. 1. Typical ials which require water addition. Installation is by
aggregates include fused alumina, tabular alumina, casting or pouring into place, vibration placement,
ISSN 0950–6608 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 con-
ventional 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 cas-
tables (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 con-
tain 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 different 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 bar-
rels,2,17–19 steel ladles2,3,7,17,18,20–27 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,17–19,29,30 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 incin-
erators,6,16,32 repairing of sliding gate plates,33 fabri-
cation of monolithic porous plugs, seating (well)
blocks and powder injection lances,33 desulphurising
and argon stirring lances,29 refractory lining of snor-
kels 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 develop-
ments 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 pro-
duction and hydration and dehydration of pure CACs
are considered before examining refractory systems
in which they are bonding phases: conventional cas-
tables, LCCs and ULCCs. The importance of particle
packing, dispersion, and rheology is highlighted as
well as the types of submicrometre powder and aggre-
gate used. Then the modern developments of cement
free, free flowing, shotcreting, and spinel and MgO-
International 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 1856.5,12,13,36–38 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 prop-
erties of compounds formed by reacting lime with
alumina were known long before the individual cal-
cium 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 carbon-
ate 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 alumin-
ate 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 con-
cretes, 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-

sumably because of its relatively high cost. The con-
cretes were crudely made and even more crudely
applied. Mixing was commonly done by hand in a
mortar box or wheelbarrow, and casting, slap trowel-
ling, 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 market-
ing 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 refrac-
toriness, erosion, and abrasion resistance.5,40
However, these had relatively simple compositions,
consisting of refractory aggregates and cement, the
latter added in sufficient amounts to give suitable
room temperature strength.18 The major disadvan-
tages 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 manufac-
tured.18,29,37,42–47 These LCCs contained at most
2·5% 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 maxi-
mum packing density, which also increases the
amount of water utilised in flow. Later, ULCCs,
characterised by an even lower lime content (<1·0%)
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 satu-
rated 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 gun-
ning, shotcasting, or shotcreting. Although the charac-
*All percentages are wt-% unless otherwise stated.
Lee et al. Castable refractory concretes 147
teristics of shotcreted LCCs were first published in
1986, it was not until after the advent of the self-
flowing technology that wet gunning became a more
effective installation tool. Pumping self-flow mixes
over significant distances, both horizontally and verti-
cally, 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), com-
bined 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 mag-
nesia, chrome ore, zircon, kyanite, mullite, silicon
carbide, alumina–magnesia spinels, and fused silica.
Cement free castables are used in numerous molten
iron and steel contact applications, where the elimin-
ation 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 bond-
ing, and phosphate bonding. Other additions to cas-
tables 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 dehy-
dration period.14,50
Classification
Refractory castables are classified by the ASTM
according to their lime content into conventional
(CaO>2·5%), low cement (2·5%>CaO>1·0%),
ultra-low cement (1·0%>CaO>0·2%), and cement
free (CaO<0·2%).14,30,38 According to this classifi-
cation, 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 vibrat-
able 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 instal-
lation is meaningless. Attempts have been made to
classify castables according to the nature of the disper-
sing phase, i.e. inorganic or organic.31 However, this
is also meaningless, since modern high performance
materials may include a combination of several addi-
tives, both organic and inorganic in nature.
Classification of modern castables is difficult.
However, a proper classification should include as
much information as possible about the chemical
International Materials Reviews 2001 Vol. 46 No. 3
148 Lee et al. Castable refractory concretes

nature, rheological behaviour, and installation calcined alumina is often the choice for the high
characteristics of the castable. purity type (HP CAC).
Alternatively, cements or CACs may be classified
according to chemical composition, forming five main
Calcium aluminate cements groups (Table 3).12 In Table 3, Group A includes
Despite the steady decrease in the amount of cement fondu and lumnite cements, while Groups B and C
used in modern high performance refractory castables, include the two alumina cements for refractories
CACs, particularly high alumina cements, continue specified in the Japanese Industrial Standards. Group
to be the most important hydraulically setting agents D includes high purity alumina cements of the
used for bonding concretes,53,54 mainly because they 70%Al O class, such as the Denka high alumina
develop high strength within 6–24 h of placement. 2 3
cement and Secar 71 (Lafarge). High purity alumina
Usually, high alumina castables require only 24 h to cements with ~80%Al O , such as the Denka super
develop 70–80% full strength when properly cured, 2 3
high alumina cement, CA–25 (Alcoa), and Secar 80
in contrast to 28 days for normal Portland cement (Lafarge) are typical of Group E. An important
concretes.53 Calcium cements are usually classified variable in these commercial cements is admixture
according to purity and Al O content. In 1972, content, e.g. Secar 71 is additive free while Secar 80
2 3
Briebach39 classified them in four major groups (like all 80% alumina cements) contains a cocktail of
(Table 1). Only cements in Group 2 were referred to additions which will confer consistent properties on
as ‘high alumina cements’, while those in Group 4 the cement but will influence rheology in a castable
were often called ‘white high alumina cements’, system based on this cement.
because of their colour. Today, however, any calcium
cement from Groups 2, 3, or 4 is often termed CAC Production techniques
or high alumina cement (HAC), or simply calcium Calcium aluminate cements are formed by reaction
aluminate (CA).38,53 of lime and alumina either by a sintering or clinker
A more recent classification of HACs38,53 is given process or from fusion.12,38 In the latter limestone
in Table 2. Relatively pure limestone (54–55%CaO, and bauxite raw materials are melted at 1450–1550°C
41–43% loss on ignition, and less than 2% total in reverbatory furnaces fired by powdered solid fuel.39
impurity) is used as the lime source for producing all The molten calcium aluminate is continuously tapped,
CA cements. The low purity cements (LP CAC) are cooled, and ground into cement. Other melting pro-
manufactured from bauxites containing up to cesses involve the use of vertical shaft and rotary
~18%Fe O and 9%SiO . Low iron (2–4%Fe O ) kilns, while electric arc resistance furnaces have also
2 3 2 2 3
and low SiO (5–7%) bauxites are used to manufac- been used where electrical energy is relatively cheap.38
2
ture the intermediate purity cements (IP CAC), while 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
Table 1 Classification and composition of calcia in the manufacture of Portland cement. The product
containing cements
is sintered at 1315–1425°C, cooled, and then ground
Cement group to cement fineness together with any additives. These
1 2 3 4 include calcined alumina to obtain the desired Al O
2 3
Calcium Calcium aluminate cements
content, gypsum or other materials to control the set,
silicate and plasticisers to improve workability.38,53 The
White high
Mineral Portland High alumina ... alumina
cement colour ranges from black to white, depending
on the impurities present and on the iron oxide
Chemical analysis, wt-% quantity and oxidation state. High purity cements
SiO 17–26 4–9 4–6 0·1–1·4
Al O
2
5–12 35–45 50–65 65–80
are white.
2 3 On sintering, the raw mix generally transforms into
Fe O 1·7–2·7 10–15 1–3 0·1–1·0
2 3
CaO 53–65 36–39 29–40 17–25 higher alumina phases as the material temperature
increases in the kiln. Both lime/alumina ratio and
temperature determine the amount and type of cal-
Table 2 Classification and properties of calcium cium aluminate phases formed during the process.
aluminate cements High lime calcium aluminates form initially with
ferrites and silicates. Uncombined lime and alumina
Type
begin to react with the high lime products and form
Low purity Intermediate purity High purity lower lime or higher alumina compounds, as predicted
Chemical analysis, wt-% by the CaO–Al O binary phase diagram (Fig. 2).
2 3
SiO
2
4.5–9·0 3·5–6·0 0·0–0·3 These reactions continue in the kiln until the mix is
Al O 39–50 55–66 70–90
2 3 completely combined as follows38
Fe O 7–16 1–3 0·0–0·4
2 3
CaO 35–42 26–36 9–28 C+AC AC A CACA CA
Surface area, m2 g−1
3 12 7 2 6
Wagner (ASTM C115) 0·14–0·16 0·16–0·24 0·22–0·30
High purity CAC sinters readily, even though very
Blaine (ASTM C204) 0·26–0·44 0·32–1·00 0·36–1·50 refractory high purity limestone and Bayer calcined
BET 0·60–1·00 0·80–5·00 0·60–18·00 alumina are used as raw materials in rotary kiln
Density, g cm−3 3·05–3·25 2·95–3·10 3·00–3·30 calcination. A 1360°C eutectic occurring at
Vicat initial set, h5min 3:00–9:00 3:00–12:00 0:30–6:00 ~50 wt%CaO/Al O (Fig. 2) enhances liquid phase
(ASTM C191) 2 3
sintering of these refractory oxides.
International Materials Reviews 2001 Vol. 46 No. 3
 Lee et al. Castable refractory concretes 149

Table 4 Typical mineral constituents of calcium

aluminate cements
Cement purity
Relative
hydration rate Low Intermediate High

Fast C A C A C A
12 7 12 7 12 7
Moderate CA CA CA
Slow CA CA CA
2 2 2
C S C S ...
2 2
C AF C A ...
4 4 F
Non-hydrating C AS C AS CA
2 2 6
CT CT A
A A ...

highest strength among the phases listed during the

2 Binary CaO–Al O phase diagram; in wt-%
2 3
The two most critical areas of cement production
are development of the clinker phases and the grind-
ing 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 affect cement hydration, but
also its reactivity with the aggregates in the concrete.
Phase composition
Typical phases present in commercial CACs, accord-
ing 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 gener-
ally occurs in large amounts (40–70%), has a rela-
tively high melting point (1600°C), and develops 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 accel-
erated 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 alumin-
4
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 prop-
erties 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

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

Group

A B C D E

Composition 1 2 3 4 5 6 7 8 9 10

SiO 3·05 8·29 4·72 4·59 2·52 3·41 0·19 0·20 0·08 0·20
2
TiO 1·95 2·08 2·16 2·09 3·23 2·49 Tr. Tr. Tr. Tr.
2
Al O 42·11 41·34 47·55 52·28 56·69 56·21 73·36 71·07 80·22 79·53
2 3
Fe O 15·55 11·32 9·52 5·34 0·89 1·88 0·35 0·09 0·15 0·22
2 3
CaO 37·46 35·24 34·82 35·27 35·75 35·39 24·46 27·70 17·63 17·12
MgO 0·65 1·17 1·19 0·35 0·43 0·53 0·30 0·33 0·35 0·44
Na O 0·08 0·10 0·06 0·10 0·08 0·08 0·18 0·21 0·66 0·51
2
KO 0·05 0·09 0·02 0·05 0·11 0·04 0·04 0·02 Tr. 0·07
2
Loss on ignition −0·21 0·80 0·35 −0·05 0·07 0·15 0·43 0·17 1·06 1·44

International Materials Reviews 2001 Vol. 46 No. 3

150 Lee et al. Castable refractory concretes

Generally, the characteristics of CACs are associ-

ated 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 stud-
ied extensively (e.g. Refs. 8, 59–65). However, system-
(a)
atic structural studies of cements are difficult. Starting
materials and hydration products are typically multi-
phase systems, which are, because of the occurrence
of metastable phases, often compositionally variable,
sensitive to experimental conditions, such as temper-
ature, duration, and intensity of mixing, and typically
only partially crystallised. For these reasons, identifi-
cation 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 (b)
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 precipi-
tation 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 hydrox-
ide. In the induction period, the hydration rate is (c)
extremely low, and the thickness of the hydrated
surface layer grows slowly. When the hydration layer
reaches a critical thickness, the stress caused by 3 Reaction schemes for a CA, b CA , and c C A
2 12 7
intruded water molecules ruptures the layer and the (after Ref. 63)
induction period terminates (the reaction as a whole
accelerates) with the formation of crystalline nuclei CAH can be detected after 6–24 h. The presence of
10
that grow by a dissolution–crystallisation mechanism C AH can be detected after 24 h.
2 8
to produce the metastable hexagonal hydrate CAH . The hydration of calcium aluminates has been
10
Depending on the initial crystallinity of the aluminate, extensively studied using a variety of methods, includ-

Table 5 Properties of CAC mineral constituents

Chemical composition, wt-% Cold crushing Setting time,
Density, strength, h5min Crystal
Mineral C A F S T , °C g cm−3 MPa Initial–final system
m
C 99·8 ... ... ... 2570 3·32 ... ... Cubic
C A 48·6 51·4 ... ... 1415–1495 2·69 15 0:05–0:07 Cubic
12 7
CA 35·4 64·6 ... ... 1600 2·98 60 7:00–8:00 Monoclinic
CA 21·7 78·3 ... ... 1750–1765 2·91 25 18:00–20:00 Monoclinic
2
C S 65·1 ... ... 34·9 2066 3·27 ... ... Monoclinic
2
C AF 46·2 20·9 32·9 ... 1415 3·77 ... ... Orthorhombic
4
C AS 40·9 37·2 ... 21·9 1590 3·04 ... ... Tetragonal
2
CA 8·4 91·6 ... ... 1830 3·38 ... ... Hexagonal
6
a-A ... 99·8 ... ... 2051 3·98 ... ... Rhombohedral

International Materials Reviews 2001 Vol. 46 No. 3


4 Typical curve for evolution of heat in calcium
aluminate cement
ing solution chemistry,68–70 X-ray diffraction,71,72
calorimetry,62,73–75 1H NMR (nuclear magnetic reson-
ance) 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 calor-
imetry (ICC). Adiabatic calorimetric studies of cal-
cium 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 70°C the length of the
induction period decreases with increasing temper-
ature.61 Once critical nuclei have been formed, mass-
ive bulk precipitation of hydrates occurs, giving rise
to a second major exothermic peak, and initiating the
hardening process.
Evolved heat of hydration differs widely depending
on the type of cement and its mineral constituents.
As indicated by Table 6, most of the hydration reac-
tions 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 affected 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
affected by temperature, and so is the setting time.
The longest time required is usually at about 30°C.
The factors influencing the evolution of heat and
setting time of CACs, particularly around 30°C, are
not yet fully understood.78 After setting, the strength
Table 6 Heats of hydration of Portland and CA
cements, cal g−1
Time, days
Cement 1 3 7 28
CA cement 77–93 78–94 78–95 ...
Portland cement 23–46 42–65 47–75 66–94
Lee et al. Castable refractory concretes 151
C2AH8+AH3
% CONVERSION
C3AH6+
2AH3
TEMPERATURE, °C
5 Temperature dependence of calcium aluminate
hydrates formation (after Ref. 65)
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 con-
ditions, and the presence of impurities, different
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 3–6 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 com-
bined8,12,38,65
<21°C CAH10 (metastable hexagonal)
CA (1)
AH (gel)
C A 3
12 7
21–35°C
CA +H CA (2)
C AH (metastable hexagonal)
CA 2 8
2 C AH (stable cubic)
>35°C 3 6 (3)
CA
AH (crystal)
3
As the temperature rises above 21°C, the metastable
hydrates CAH and C AH change into the more
10 2 8
stable compounds, C AH and AH .8,12 The tran-
3 6 3
sitional crystalline change from one calcium alumin-
ate hydrate to another is commonly referred to as
‘conversion’. Figure 5 summarises the changes in prin-
cipal 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
International Materials Reviews 2001 Vol. 46 No. 3
152 Lee et al. Castable refractory concretes

Formation of stratlingite avoids the conversion reac-

tion 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 effect on the high temperature microstructural
development, see the section ‘Calcined alumina’
below.

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 buffers 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’
a 18 h, C AH hexagonal plates; b 11 d, C AH deltoid icositetrahedra below, the most common additions to calcium alum-
2 8 3 6
6 Hydrate microstructure in CAC with water/ inate containing castables control the setting charac-
cement ratio 2 at ambient temperature;80 teristics of the cement. They are the so-called set
marker 10 mm retarders and accelerators. Among the retarders, the
following are significant: citric84–86 and phosphoric8
acids, diluted acetic acid,38 boric acid,60,87 borax,8,38
stable hydrates (AH and C AH ) at higher curing
3 3 6 sodium citrates60,88 and gluconates,60 hydroxy-
temperatures produces greater porosity and larger
carboxylic acid salts,8,38 saccharides,8 magnesium and
pore sizes than when the metastable and less dense
barium hydroxides,38 sodium chlorides and sul-
hydrates (CAH and C AH ) are formed at lower
10 2 8 phates,38 starch, sugar, sea water, and many other
temperatures. While this gives lower green strengths65
acids and acidic compounds.38 The most commonly
it also gives coarse, permeable hydrate phases so that
cited set accelerators are: lithium salts and carbon-
vapour species can escape on drying. The imper-
ates,38,88 calcium hydroxide,38,60 Portland
meable AH gel phase developed at low curing tem-
3 cement,38,51 slaked lime,66 hydratable aluminas,51
peratures increases the danger of explosive spalling
sodium and potassium carbonates,38 sodium sili-
on drying due to steam build up. For this reason,
cates,38 and many other alkalis and alkaline com-
refractory CAC castables are generally cured above
pounds.38 It has been suggested88 that the combined
27°C. Best practice for safe heating and maximum
use of set retarders and accelerators is more effective
strength development is to cure for at least 24 h at
and allows better control of the hydration process.
30–38°C covered in an impermeable membrane to
The reaction mechanisms of set retarders and accel-
maintain a humid environment for hydration, fol-
erators are still unclear,8 but it is generally agreed
lowed by a 24 h air cure with the surface exposed to
that retarders influence the kinetics of hydration by
30–38°C.81 The increase in porosity and its effect on
slowing down the dissolution of the anhydrous cement
strength are also heavily influenced by original total
particles.89 It is believed that accelerators influence
water/cement ratio.
mainly the dormant period of hydration. Lithium
The presence of other phases such as microsilica
salts are mostly used as accelerators, and it is believed
or reactive magnesia along with CAC in castables is
that lithium ions interact with Al(OH)− to precipitate
known to influence the hydration mechanism.64,82 4
insoluble lithium aluminate hydrate, thereby increas-
Pantjadarma64 determined that stratlingite (gehlenite
ing the Ca2+/Al(OH)− ratio in the solution. Rapid
hydrate, C ASH ) formed with microsilica present 4
2 8 hydrate formation is then promoted, and the setting
having the same platey morphology as C AH sug-
2 8 time is consequently reduced.89
gesting it formed by reaction of silica and C AH .
2 8
Dehydration and firing
Table 7 Properties of CA cement hydrates
Strength loss is known to occur in hardened calcium
Chemical composition, wt-%
Crystal Density, aluminate pastes as the metastable hexagonal CAH
10
Hydrate CaO Al O
2 3
HO
2
system g cm−3 phase dehydrates through the hexagonal C AH
2 8
CAH 16·6 30·1 53·5 Hexagonal 1·72 transition phase into the stable cubic C AH .12,38,51,90
10 3 6
C AH
2 8
31·3 28·4 40·3 Hexagonal 1·95 This loss of strength can best be appreciated by
C AH
3 6
44·4 27·0 28·6 Cubic 2·52 considering the morphological and volume changes
AH ... 65·4 34·6 Hexagonal 2·42
3 accompanying this conversion. When CAH is
10
International Materials Reviews 2001 Vol. 46 No. 3

allowed to form during low temperature curing, the
metastable hexagonal prisms (density 1·72 g cm−3)
and gel (2·42 g cm−3) solidify and eventually will
convert to the stable cubic (2·52 g cm−3) type with
time and/or temperature. The gross restructuring
from H O loss leading to pore formation and nominal
2 Conventional castables consist of graded refractory
50% volume shrinkage on conversion of CAH to
10
the denser C AH and a-AH are disruptive to a rigid
3 6 3 cements described in the section above. The properties
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
differential thermal analysis (DTA), derivative therm-
ogravimetry (DTG), and differential scanning calor-
imetry (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 (50–70°C). 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 described for CACs in the section ‘Dehydration and
C AH , in its turn, often shows a stepwise dehy-
3 6
dration process, usually indicated in the DTA curve
by two endothermic peaks, one around 300°C and
the other close to 500°C. It has been claimed that the
first 4·5 molecules of water are lost in one step, and
the next 1·5 in another.91 The possibility that the
1·5H O phase (C AH ) might represent some inter-
2 3 1·5
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 1·5
constitutes a step in the dehydration of C AH at
3 6
low partial pressures of water.93 AH gel and gibbsite
3 eventually, if enough free alumina is present, CA
usually dehydrate between 210 and 300°C (Table 8)
but they may otherwise convert to boehmite (AH),
which only dehydrates at ~530–550°C.
The compounds formed during hydration of CACs
dehydrate up to ~550°C.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 1500°C.12 The
microstructural changes associated with these reac-
tions and the morphologies of the phases formed were
studied in detail by Parker.95 She determined that on
drying at 110°C, CAH and C AH either dehy-
10 2 8
drated to amorphous products or, if water was pre-
sent, converted to C AH and gibbsite. Firing above
3 6
300°C dehydrated the pastes completely and reduced
their strength due to increased porosity and pore
growth. Pastes fired to 900°C and dried pastes were
morphologically similar while above 900°C CA crys-
tallised and sintering began to occur leading to
Table 8 Dehydration temperature of CA cement
hydrates
Hydrate CAH C AH C AH
10 2 8 3 6
Dehydrating temperature, °C 100–130 170–195 300–360
Lee et al. Castable refractory concretes 153
coarser pores in the plates and cuboids which sub-
sequently collapsed. Sintering led to ceramic bonding
and improved strengths.
Conventional castables
aggregates bonded with the aluminous hydraulic
of these concretes depend largely on the choice of
refractory aggregate and hydraulic cement.19 They
contain ~15–30%CAC,18,29,33,37 this amount being
necessary to achieve satisfactory strength at low and
intermediate temperatures though it makes the mater-
ial thirsty. The 8–15% water generally added during
processing is mainly used to develop the hydraulic
cement bond (6–10%) and to make the concrete flow
(2–6%), allowing its proper installation. However, a
relatively large amount of water (0–5%) 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
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 effect 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
6
(Fig. 7). At room temperature alumina gel, hydrated
calcium aluminates, and free alumina coexist.96 On
heating to 200°C dehydration occurs and by 400°C
C A starts to form from amorphous dehydrated
12 7
calcium aluminates. At 900°C elongated CA forms
(Fig. 7a) from reaction of alumina and C A . At
12 7
1000–1200°C CA reacts with alumina to form coarse
and globular CA (Fig. 7b) while at >1300°C CA
2 2
reacts with alumina to form hexagonal platelets of
CA (Fig. 7c–f ). 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 per-
meability of castables at temperatures below 21°C is
ascribed to the alumina gel formed upon curing.53
The open porosity of a conventional castable dried
at 110°C is generally about 9–17%,33 but can be as
low as 8%.18 Although some of this porosity is due
AH
to entrapped air bubbles, most of it is caused by the
3 excess water added on mixing. On heating, the
210–300
hydraulic bond is first modified, as conversion takes
International Materials Reviews 2001 Vol. 46 No. 3
154 Lee et al. Castable refractory concretes

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

7 Microstructural evolution on firing conventional castable matrix96

place, and then destroyed by the dehydration process.
During this textural modification, the pore size distri-
bution 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 conven-
tional refractory concretes fired at 1000°C generally
varies from 22 to 26%, depending on the type of
aggregate used.
Second, conventional castables show a character-
istic drop in strength at intermediate temperatures
(often quoted to be between 538 and 982°C7), 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

70%Al O CAC 80%Al O CAC
Temperature, 2 3 2 3
°C C A CA CA CA A C A CA CA CA A
12 7 2 6 12 7 2 6
500 X ... ... ... X ... ... ... ... X
600 X ... ... ... X ... ... ... ... X
700 X ... ... ... X X ... ... ... X
800 X ... ... ... X X X ... ... X
900 X X X ... X X X X ... X
1000 X X X ... X ... X X ... X
1100 ... X X ... X ... X X ... X
1200 ... X X ... ... ... X X ... X
1300 ... X X ... ... ... X X ... X
1400 ... X X ... ... ... ... X X X
1500 ... X X ... ... ... ... X X X

International Materials Reviews 2001 Vol. 46 No. 3


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 sched-
ule. C AH becomes thermodynamically unstable
3 6
above ~292°C 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 press-
ure, 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 temper-
4 3 3
atures several hundred degrees above their equi-
librium stability limit without much effect.93 Thick
(tens of centimetres) linings may develop hydrother-
mal 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 900°C, significant sintering of calcium aluminate
crystallites themselves and with neighbouring alumina
crystals only occurs at temperatures close to 1100°C.94
Early attempts to accelerate the formation of a cer-
amic 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 1000°C 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 CaO–Al O –
2 3
SiO (CAS) ternary system which may encourage
2 Two other French patents in 1976 and 197747
crystal formation (e.g. mullite or spinel, see the sec-
tions ‘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
70–80%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 prop-
erties 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 behav-
iour at the service temperature which is more import-
ant 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 cas-
tables. Reducing the amount of cement without spoil-
ing other properties of the material proved difficult
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.
Lee et al. Castable refractory concretes 155
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 mechan-
ical resistance was insufficient for compositions with
less than 10% cement.33 Refractory castables with no
more than 5–8% 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 ~2·5–4% fine (<50 mm, but ideally less
than 1 mm) clay minerals and 0·01–0·30% defloccu-
lants (such as alkali metal phosphates and carbon-
ates). 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 cor-
rosion resistance, compared with conventional cas-
tables, 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 spal-
ling since the outer layers closed off 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 450°C, 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 difficult, especially in thick installations.14
further reduced the cement content of the castables
to less than 3%, again by using dispersing additives,
such as sodium tripolyphosphate (0·01–0·05%), 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 0·1 to 0·01 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 coagu-
lation 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 resist-
ance.11,99–101 Low and ultra-low cement castables
usually require 3–7% 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
International Materials Reviews 2001 Vol. 46 No. 3
156 Lee et al. Castable refractory concretes
8 Relations between particle packing, dispersion,
and rheology
to the new range of LCCs and ULCCs, while incorpo-
rating the third further improved the overall under-
standing 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 main-
taining strength. A major breakthrough in the devel-
opment of this technology was the realisation that
this could be accomplished by improving the packing
density of the material. More efficient particle packing
reduces the maximum size of the interstices between
particles. For a size distribution which packs more
efficiently, less of the liquid is segregated in large
interstices and more of it is effectively mobilised in
flow. The packing density of about 62% for a monos-
ize system can be increased above 75% by adding a
specific proportion of a finer size that packs efficiently
in the interstices among the coarse fraction.102
However, the idea of reducing the water require-
ment 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 includ-
ing sodium carbonates,8,89,102 sodium silicates8,102
and borates,102 sodium pyrophosphates,8,102
hexametaphosphates44,60,85,103,104 and tripoly-
phosphates,85,103,105,106 ammonium102,104 and
sodium102,105,106 polyacrylates, sodium sulphon-
ates,102,106 sodium citrates38,102 and gluconates,38 and
many others offered commercially under proprietary
names such as Darvan 7S (organic polyacrylate poly-
mer) and Castament FS10 (polyglycol based poly-
mer).89 These deflocculants are used separately or in
combination with each being used to deflocculate a
International Materials Reviews 2001 Vol. 46 No. 3
particular type of particle, often in small amounts,
usually between 0·05 and 0·5%.
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
powder–water 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 effective
stress, or interparticle stress, is independent of press-
ure 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 mechan-
ical interactions between particles. In a nearly close-
packed system, initial flow produces significant con-
tact stress between particles. Volume dilation of the
system must occur to accommodate shear flow. In
these systems the effective stress and the shear resist-
ance 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 (10−1 s−1) to the very high shear rates
characteristic of spraying (105 s−1), through the inter-
mediate rates usually used in pumping and mixing
operations (1–103 s−1). 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 concen-
tration) 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 sig-
nificant pseudoplastic behaviour at high shear rate,
including ultrafine alumina (<0·5 mm). Dispersion of
agglomerates, by the use of deflocculants, or modifi-
cation of the particle size distribution to produce
additional fines may also extend the range of shear
rate before shear thickening is observed in the cast-
able. As for the fines, it is generally believed that a
 Lee et al. Castable refractory concretes 157

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 effective 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, sili-
con 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 material’s purity and pH have been
shown to have drastic effects on LCCs, with impurit-
ies, 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, classify-
ing, 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
~0·15 mm. These spheres are the building units of
primary agglomerates which consist of a few spheres
bonded together by material bridges. Thus, the effec-
tive size distribution becomes rather wide in the
microsilica has a relatively low bulk density
(0·2–0·45 g cm−3) and is readily dispersed in refrac-
tory concretes improving casting properties. Densified
microsilica contains loosely bonded secondary
agglomerates which increase the bulk density
(0·5–0·6 g cm−3) and improve the handling character-
istics of the material, but it requires a high intensity
wet mixing to assure complete dispersion. There is
no difference 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 refractor-
ies 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 tra-
ditionally been found to be more effective 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 20–30% to 8–16% after firing
at 1000°C, 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
effect 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 progress-
ively over a wider temperature range. Because of this,
it has been argued that castables with a ‘pseudozeo-
lithic’ 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 drasti-
Table 10 Typical properties of microsilica
Mineral 960 971 983

submicrometre range. This wide particle size distri- Typical chemical composition,
bution is believed to bring beneficial effects, as it wt-%
SiO 97·00 96·00 97·50 98·30
increases the packing efficiency and enhances the Al O
2
0·40 0·40 0·40 0·20
workability of the concrete.112 2 3
CaO 0·15 0·20 0·20 0·20
High purity microsilica from the production of MgO 0·30 0·30 0·10 0·07
metallic silicon is usually preferred for refractories Fe O
2 3
0·10 0·10 0·10 0·05
Na O 0·10 0·10 0·10 0·04
applications.43,44 In refractory castables, use of high 2
KO 0·20 0·40 0·30 0·25
quality, high purity microsilica is almost mandatory, 2
PO ... 0·10 0·10 0·06
2 5
since low purity microsilica reduces flow and increases SO ... 0·10 0·10 0·01
3
water requirement for placement.113 The material is C ... 1·80 0·50 0·40
highly reactive in cementitious and ceramic bond Loss on ignition (750°C) ... 2·00 0·60 0·60
Median particle size, mm 0·15 ... ... ...
systems, leading to improved ceramic bonding (form- Surface area, m2 g−1 18–28 22 20 ...
ing, e.g. mullite and forsterite) at reduced firing tem- pH 6–8 6·5 6·0 5·3
peratures both in high alumina and magnesia Bulk density, g cm−3
based products. Microsilica is usually available in Undensified ... 0·25 0·40 0·40
Densified ... 0·60 0·55 ...
undensified (U) and densified (D) forms. Undensified
International Materials Reviews 2001 Vol. 46 No. 3
158 Lee et al. Castable refractory concretes
cally change the properties of the system. Because of
its high specific surface area (20 m2 g−1), 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
affect the casting and setting properties of the castable.
When microsilica is added to a refractory contain-
ing 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 seques-
tering 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 (40–60°C) to form
C ASH (see the section ‘Hydration’ above). When
2 8
heated above 210°C, the chemically bonded water is
released, and C ASH dehydrates and becomes
2 8
amorphous. From ~1000°C upwards silicate liquid
may form and gehlenite (C AS) and anorthite (CAS )
2 2
crystallise.118,119 At these temperatures and up to
~1200°C, microsilica containing castables exhibit
superior properties compared with microsilica free
castables, including a reduction in porosity of about
5–8% 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 1200°C, the hot strength deteriorates,
depending on the amounts of cement and microsilica,
due to eutectic liquid formation in the C–A–S ternary.
However, it has been observed that, in high alumina,
microsilica containing LCCs and ULCCs, the hot
strength sometimes increases significantly above
1300°C, reaching its maximum around 1400°C, only
to drop again at 1500°C.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 1400°C,
the bond phase of the castable reacts and produces a
viscous liquid formed mainly from cement and micro-
silica. Within a few hours, the liquid starts to dissolve
alumina, which goes into solution with silica and
lime; the liquid becomes saturated, and mullite pre-
cipitates. 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
diffusion 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
1·5% cement (0·27%CaO), strengthening due to the
formation of mullite is only observed for microsilica
contents above 6%. For castables with 7·5% cement,
at least 10% microsilica is necessary, but since there
is always some liquid present in the castable, and this
International Materials Reviews 2001 Vol. 46 No. 3
increases with the cement content, the high cement
castables usually show lower hot strength.120 The
subsequent drop in strength observed at 1500°C,
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
1500°C, this did not change the general trend, since
the strength also dropped at 1500°C 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 C–A–S 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 C–A–S 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 effects to the rheology and
packing of the system, is detrimental to the hot
strength at temperatures around and above 1500°C,
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 0·5%. But so far this has only proven feasible
with the simultaneous addition of cement (0·5%) and
hydraulic alumina (0·5%), 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
1500°C 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
0·1%, usually between 0·18 and 0·55%, and
~99·0–99·5%Al O . The second category contains
2 3
calcined aluminas, sometimes referred to as ‘low soda’,
with an alumina content of about 99·7% and less
than 0·1% soda. The third category includes high
purity calcined aluminas with at least 99·9%Al O .
2 3
Almost all calcined aluminas, including those for
refractory applications, are produced by heat treat-
ment 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 (95–99%), but these agglomer-
ated 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 com-
pacted and sintered into ceramic products. Sintering
temperatures required to densify completely ceramics
made from fine superground aluminas are usually
200°C lower than those made from regular ground,
coarser aluminas. These reactive aluminas are not,
however, capable of hydraulic activity to form chemi-
cal bonds at ambient temperatures. Hydratable alum-
inas (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 alum-
inas have traditionally been recommended for alum-
ina 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 affect the dispersion of alumina, increas-
ing the viscosity,111 and the hydration of cement,
shortening the induction period,74 but also the physi-
cal characteristics such as crystal shape and size,
particle size distribution, specific surface area, a-Al O
2 3
content, compacting behaviour, and sintering reactiv-
ity. 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 different particle size distri-
butions may further contribute to reduce the water
requirement for placement.23 The use of calcined
aluminas with multimodal particle size distributions
may have similar effects 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
Lee et al. Castable refractory concretes 159
crystal size increases, green density increases. Also, as
the crystal size distribution is broadened, green den-
sity increases. High green density minimises shrinkage
during sintering. Coarser crystalline aluminas exhibit
minimum shrinkage at 1500°C, 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, includ-
ing 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 com-
mercial 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 mul-
tiple 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 investi-
gated. 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 60–85% of the
castable mix, and its chemical composition and physi-
cal characteristics significantly affect the final prop-
erties 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 coefficient, 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 refrac-
toriness of the binary CaO–Al O system (Fig. 2),
2 3
and this also accounts for its widespread use in
cement containing castables.
International Materials Reviews 2001 Vol. 46 No. 3
160 Lee et al. Castable refractory concretes

Table 11 Typical properties of reactive calcined aluminas43,115

Type of alumina

16SG 152SG A17 1000SG 3000FL RA7 RA10 RA15

Composition, wt-%
Al O 43,115 99·7 99·7 99·7 99·7 99·7 ... ... ...
2 3
SiO 0·03 0·04 0·03 0·02 0·02 ... ... ...
2
Fe O 0·01 0·04 0·01 0·02 0·02 ... ... ...
2 3
Na O 0·08 0·08 0·08 0·08 0·08 ... ... ...
2
Crystal size, mm 0·4 1·5 3·25 0·4 3·25 ... ... ...
Particle size, mm 0·5 1·5 3·0 0·5 3·0 1·1 2·1 2·7
Surface Area, m2 g−1 10 3 3 10 3 3 2·2 3·7
Green density, g cm−3 2·15 2·25 2·50 2·15 2·50 ... ... ...
Fired density, g cm−3 3·91 3·84 3·75 3·91 3·75 3·50 3·40 3·60
Compaction pressure, MPa 345 345 345 345 345 ... ... ...
Sintering
Temperature, °C 1540 1620 1750 1540 1750 1650 1650 1650
Time, h 1 1 1 1 1 ... ... ...

White fused alumina (WFA) is produced by fusion
of calcined alumina in an electric arc resistance fur-
nace, 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 crys-
2 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
3·40–3·65 g cm−3, with characteristic closed spherical
porosity typical of a fully sintered ceramic with sec-
ondary 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 super-
fine 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 com-
positions 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, disper-
International Materials Reviews 2001 Vol. 46 No. 3
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 difficult,
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 magni-
tude ultimately exceeds the material strength.8 It is
also believed that the internal vapour pressure
depends largely on the curing temperature and mater-
ial 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 0·5% and
usually between 0·05 and 0·2%) 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 temper-
ature, preventing catastrophic failure of the instal-
lation. 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 per-
meability.99 It has also been suggested that the heat
 Lee et al. Castable refractory concretes 161

Table 12 Composition (wt-%) of low and ultra-low cement castables

Ref. 44 105 105 101 80 104 83 83 83

Spinel ... ... ... ... ... ... ... ... 23

Fused alumina ... ... 71·5 84·0 71·0 ... ... ... ...
Tabular alumina ... ... ... ... ... 78 80 80 60
Calcined bauxite 82·5 68·0 ... ... ... ... ... ... ...
Kyanite ... 10 ... ... ... ... ... ... ...
Microsilica 6 6 10 8 5 ... 5 ... ...
Calcined alumina ... ... ... 7 9·5 ... ... ... ...
Reactive alumina 10 10 17 ... 8·5 17 10 15 11
Dispersing alumina ... ... ... ... ... 1 ... ... ...
Hydraulic alumina ... ... ... 0·5 ... ... ... ... ...
CA cement 1·3 6 1·5 0·5 6 5 5 5 6
SHMP 0·18 0·20 ... ... ... ... ... ... ...
Polyacrylate (Darvan) ... ... 0·05 0·05 0·05 ... 0·05 ... ...
Polyglycol (Castament) ... ... ... ... ... ... ... 0·5 0·05
Sodium carbonate ... ... ... ... ... ... 0·005 0·05 0·005
Citric acid ... ... ... ... 0·05 ... 0·015 0·15 0·012
Water, wt-% 5 5 4 4·1 4·1 4·0 5·0 5·0 5·0

released during the exothermic reaction of aluminium Properties

with water is effective 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, effecting the
aluminium reaction, setting, and hydrogen generation.
Whatever the case, this technique requires that pre-
cautions be taken to vent the H properly to prevent
2
formation of explosive atmospheres.
In general, on firing LCCs and ULCCs the reac-
tions described for pure CAC (see the section
‘Dehydration and firing’ above) and for conventional
castables (see the section ‘Microstructural develop-
ment’ 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 C–A–S and C–M–A–S
phase diagrams indicate the phases expected at equi-
librium for the local matrix composition.125,126 If the
bond does not include fine silica low cement, compos-
itions 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 effect on
microstructural evolution at high temperature (above
1000°C). Sarpoolaky et al.127 examined LCCs with
different aggregates (TA, WFA, BFA, and spinel) but
a similar CAC/fine alumina bond. On firing at 1000°C
the bond was similar in all four samples consisting
predominantly of alumina, CA, and CA . However,
2
after firing at 1600°C 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 effects on the
corrosion mechanisms in these refractories.
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 cas-
tables vary with the temperature. A conventional
castable has an open porosity of about 9–17% after
drying and ~20–30% after heat treatment at 1000°C.
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 instal-
lation parameters and variations in water addition
and casting conditions, such as the ambient temper-
ature, may affect 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 elimin-
ation 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.37,51,52,128–130
International Materials Reviews 2001 Vol. 46 No. 3
162 Lee et al. Castable refractory concretes
Among the different binding systems for non-
cement 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
1–2 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 0·5%, 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 200–300°C, because of
the impervious structure. Besides, curing of a-alumina
containing, cement free castables must commence at
temperatures above 18°C, 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 difficult
or even impossible. Low and ultra-low cement cast-
ables are often the first technical choice, but whether
these materials can be satisfactorily installed is not
always immediately apparent. Among the many fac-
tors that affect the quality of the installation, and of
course the performance of the lining, are the following:
inefficient mixing, excess water additions, difficult
placement, and inexperienced personnel.17 Flow of
LCCs and ULCCs is usually promoted by internal
or external vibration, since these materials are thixo-
tropic 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 instal-
lation associated with the vibration placement, a new
class of high performance LCCs and ULCCs, charac-
terised 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 aggre-
gates and by the judicious choice of defloccu-
International 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 4·5–8·0%, 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 ver-
sions had high cement levels, and were simply
improved flow, conventional castables. Modern self-
levelling 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 tech-
nology, 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
30°C being particularly harmful and detrimental to
the installation quality;31 differences in plant sites and
applications, which require different 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 gener-
ation 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 affects
the mechanical strength and corrosion resistance of
these materials.115
Studart and co-workers recently outlined develop-
ment of castables which are both cement free and
self-flowing achieved by close control of matrix
particle size distribution and rheology.110,132–134
Shotcreting self-flowing castables
Shotcreting, wet gunning, or shotcasting, is an instal-
lation 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.16,135–138 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 effective instal-
lation 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 effort was made by
pump manufacturers to design pumps that would
provide the necessary pressure to transport heavier,
more viscous refractory materials through the rela-
tively 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 h−1. The pump used
successfully on most jobs has dual reciprocating
hydraulically powered 75 mm dia. material cylinders,
whose pistons are capable of pressurising the refrac-
tory 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 acceler-
ator, 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 stiffens 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 conven-
tional lightweight products, though the technique is
becoming more attractive to non-cement systems.
However, regardless of the binding system, any self-
flowing 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 tend-
ency to segregation. Besides, after experiencing press-
ures 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 effective. Finally, the set activator, or accelerator,
must fully penetrate and activate the castable to
provide sufficient and rapid stiffening when the mater-
ial is sprayed on the walls.
The accelerator is actually a liquid system contain-
ing a soluble set activator. Ideally, it should be
Lee et al. Castable refractory concretes 163
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 stiffen
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 con-
cern with steel cleanliness and the efficiency of steel
desulphurisation achieved in secondary steelmaking,
has led to the development of alumina–spinel and
alumina–magnesia castable compositions. First,
alumina–spinel materials, made up of a mixture of
WFA or tabular alumina and MgAl O spinel aggre-
2 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 off in service.24 Recently, self-forming, or in
situ alumina–magnesia spinel castables became avail-
able 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
2·2 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 con-
taining 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 alumina–reactive MgO mixtures also leads
to large heat evolution via formation of hydrotalcite
type phases (Mg Al CO (OH) .4H O).82 A deleteri-
6 2 3 16 2
ous volume increase is also associated with hydrotalcite
formation.
International Materials Reviews 2001 Vol. 46 No. 3
164 Lee et al. Castable refractory concretes
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 2·45% predicted from molar volumes.143 The
volume expansion from direct spinel formation
together with the calcium aluminates (CA at high
6 slag penetration resistance.120 One way to overcome
temperature) and alumina provides a dense matrix
system.20,21,24 However, this depends on several fac-
tors, such as the amounts and particle size distri-
butions of the powders, the presence of impurities,
and the amount of liquid phase formed at high
temperatures.24,144 If these are not properly con-
trolled, the volume change associated with spinel
formation may cause an overall bulk volume expan-
sion of the lining, rather than a densification of the
microstructure. Fuhrer et al.98 determined that spinel
formation occurs between 1200 and 1400°C with a
tuber-like morphology interlinked with CMAS phases
and CA platelets derived from the CAC. In these
6 low mechanical strength, become more serious than
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 prop-
erties 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 micro-
structure of a commercial in situ spinel ULCC reveals
several morphologies of in situ spinel on firing. At
1200°C 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 alumina–spinel 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
International Materials Reviews 2001 Vol. 46 No. 3
match for the magnesia–carbon 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 thermo-
mechanical 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 forster-
ite (M S) bond.148
2
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 suffer,
2 3
for example, from poor corrosion and spalling resist-
ance especially in a basic slag environment.
Unfortunately, the newly developed basic (MgO and
MgO–CaO) castables also have poor spalling and
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
in denser, pressed carbon containing bricks so that
more effective additives (antioxidants) are needed.
Although aluminium and its alloys are very effective
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 effort is underway to solve these
problems and develop carbon containing castables.149
References
1. . : Post Congress Seminar of UNITECR ’95, Kyoto,
Japan, 1995, Technical Association of Refractories Japan,
103–132.
2. . , . , and . : Adv. Ceram., 1984,
13, 1–20.
3. . . . . : Post Congress Seminar of UNITECR
’95, Kyoto, Japan, 1995, Technical Association of Refractories
Japan, 25–47.
4. . . : Post Congress Seminar of UNITECR ’95, Kyoto,
Japan, 1995, Technical Association of Refractories Japan,
67–82.
5. . . : Adv. Ceram., 1984, 13, 46–66.
6. . . : in ‘Engineered materials handbook’, Vol. 4,
‘Ceramics and glasses’, 910–917; 1991, Materials Park, OH,
ASM International.
7. . , . . , and . . : Adv. Ceram.,
1984, 13, 257–273.

8. . , . , . , . , and . :
T aikabutsu Overseas, 1989, 9, (1), 10–25.
9. . , . , . , and . : Proc.
UNITECR ’95, Kyoto, Japan, 1995, 205–213.
10. . , . , . , and . :
Proc. UNITECR ’95, Kyoto, Japan, 1995, 181–188.
11. . : Br. Ceram. T rans., 1994, 93, (6), 252–254.
12. . : ‘Technology of monolithic refractories’; 1984,
Tokyo, Plibrico Japan Co. Ltd.
13. . .  and . . : J. Am. Ceram. Soc., 1998, 81, (6),
1385–1410.
14. . . , . . , and . . : Am. Ceram. Soc.
Bull., 1990, 69, (10), 1690–1693.
15. . . , . . , and . . : Proc.
UNITECR ’93, São Paulo, Brazil, 1993, Asociación
Latinoamericana de Fabricantes de Refractarios, 527–538.
16. . , r, . . , and . . : Proc.
UNITECR ’97, New Orleans, LA, 1997, American Ceramic
Society, 531–544.
17. . .  and . : Steel T imes, January 1995,
15–17.
18. . , . . , and . . : Adv. Ceram., 1984,
13, 274–284.
19. .  and . . : Adv. Ceram., 1984, 13,
230–244.
20. . , . , . , . ,
. , and . : Proc. UNITECR ’95, Kyoto,
Japan, 1985, Technical Association of Refractories Japan,
203–212.
21. . , . , . , and . : Proc.
UNITECR ’97, New Orleans, LA, 1997, American Ceramic
Society, 165–173.
22. . , . , . , and . :
Steel T echnol. Int., 1995–96, 101–104.
23. . , . , . , . , . ,
. , . , and . : T aikabutsu Overseas, 1997,
17, (1), 53–57.
24. . , . , . , and . :
T aikabutsu Overseas, 1997, 17, (3), 39–43.
25. . , . . , . . , . . , . .
, and . . : 39th Int. Colloq. on Refractories
in Stahl Eisen Spezial, 1996, 10, 104–107.
26. . , . , . , and . : 39th
Int. Colloq. on Refractories in Stahl Eisen Spezial, 1996,
10, 108–111.
27. . , . , and . : Proc. Int. Symp. on
‘Advances in refractories for the metallurgical industries II’,
Montréal, Québec, 1996, 125–133.
28. . , . , . , and . :
T aikabutsu Overseas, 1997, 17, (3), 29–33.
29. . : Adv. Ceram., 1984, 13, 21–45.
30. .  and . : T aikabutsu Overseas, 1997, 17,
(3), 45–49.
31. . : Am. Ceram. Soc. Bull., 1995, 74, (9), 117–118.
32. . .  and . . : Proc. UNITECR ’89,
Anaheim, CA, 1989, American Ceramic Society, 1194–1206.
33. . , . . , and . . -: Proc.
Int. Conf. on ‘Refractories’, Tokyo, Japan, 1983, Technical
Association of Refractories Japan, 589–606.
34. . , . , . , . , and . :
Proc. UNITECR ’95, Kyoto, Japan, 1995, Technical
Association of Refractories Japan, 277–284.
35. . , . , . , . , . , and
. : T aikabutsu Overseas, 1994, 14, (2), 32–37.
36. . . : in ‘Refractory concrete’, 1–10; 1987, Detroit,
MI, American Concrete Institute.
37. . . , . . , and . : Proc. ALAFAR 25,
Bariloche, Argentina, 1996, 75–84.
38. . .  and . ac: in ‘Alumina chemicals –
science and technology handbook’, 171–183; 1990, Westerville,
OH, American Ceramic Society.
39. . . : T rans. J. Br. Ceram. Soc., 1972, 71, 153–158.
40. . ac, . , and . : Proc. UNITECR ’95,
Kyoto, Japan, 1995, Technical Association of Refractories
Japan, 179–186.
41. . . , . . , and . . : Adv. Ceram.,
1984, 13, 21–45.
42. . . , . , . . , and
. . : Proc. UNITECR ’97, New Orleans, LA,
1997, American Ceramic Society, 1305–1314.
Lee et al. Castable refractory concretes 165
43. . : Am. Ceram. Soc. Bull., 1994, 73, (5), 68–73.
44. . : Proc. UNITECR ’93, São Paulo, Brazil, 1993,
Asociación Latinoamericana de Fabricantes de Refractarios,
583–594.
45. . .  and . . : Proc. ALAFAR 25, Bariloche,
Argentina, 1996, 45–54.
46. .  and . : US Pat. 3 802 894, April 1974
(French Pat. Appl. 6 934 405, 1969).
47. . . , . , and . . : US Pat. 4 111 711,
September 1978 (French Pat. Appls. 7 622 344, 1976 and
7 714 717, 1977).
48. . . , . , . , .  , and
. : Proc. UNITECR ’91, Aachen, Germany, 1991,
German Refractories Association, 264–266.
49. . . : T aikabutsu Overseas, 1987, 9, (1), 2–9.
50. . . , . . , . . , and . . :
Proc. UNITECR ’93, São Paulo, Brazil, 1993, Asociación
Latinoamericana de Fabricantes de Refractarios, 572–582.
51. .  and . : Proc. UNITECR ’95, Kyoto,
Japan, 1995, Technical Association of Refractories Japan,
309–316.
52. .  and . : Proc. UNITECR ’95, Kyoto, Japan,
1995, Technical Association of Refractories Japan, 317–324.
53. . ac, . . , . . , and . . :
Ceram. Sci. Eng. Proc., 1983, 4, (1–2), 46–65.
54. . . , . ac, and . . : Interceram.,
1982, 31, (5), 519–523.
55. . , . , and . : Proc. UNITECR ’97,
New Orleans, LA, 1997, American Ceramic Society,
1273–1282.
56. . , . . , and .  : Bull. Sp. Ceram.
Glass Soc., 1976, 15, (5), 319–321.
57. . . , . , and . . : Am. Ceram. Soc.
Bull., 1987, 66, (3), 583.
58. . , . . , and . . : J. Mater. Sci., 1996, 31,
3223–3229.
59. . .  and . . : Proc. UNITECR ’97, New
Orleans, LA, 1997, American Ceramic Society, 1325–1333.
60. . , . , and . : Proc. UNITECR ’95,
Kyoto, Japan, 1995, Technical Association of Refractories
Japan, 301–308.
61. .  and . . : J. Am. Ceram. Soc., 1993, 76,
(2), 409–416.
62. . , . , . , and . . : Proc.
UNITECR ’97, New Orleans, LA, 1997, American Ceramic
Society, 109–116.
63. . .  and . . : Br. Ceram. T rans. J., 1982, 81,
(5), 35–42.
64. . : ‘Microstructural development and calcium
aluminate bonding in refractory castables’, PhD thesis,
University of Sheffield, 1995.
65. ‘Calcium aluminate cements in construction: A re-assessment’;
1997, Slough, UK, The Concrete Society.
66. . , . , and . : J. Am. Ceram. Soc., 1989,
72, (11), 2136–2141.
67. . . : ‘The chemistry of cement and concrete’, 3rd edn;
1970, Glasgow, UK, Edward Arnold.
68. .  and . -: Proc. UNITECR
’89, Arnheim, CA, 1989, American Ceramic Society,
1157–1170.
69. . , . , and . : J. Am. Ceram. Soc., 1986,
69, 361–364.
70. . . , . . , . , . . , and
. . : J. Mater. Sci., 1985, 20 2853–2860.
71. . .  and . . : Cem. Concr. Res., 1988,
18, 311–320.
72. . .  and . . : Cem. Concr. Res., 1989,
19, 289–294.
73. . , . , . , and . : Br. Ceram.
T rans. J., 1985, 84, 25–28.
74. . , . , . , . , . .
, . , and . : Proc. UNITECR ’95,
Kyoto, Japan, 1985, Technical Association of Refractories
Japan, 313–320.
75. . , . , . , . , . ,
. , and . : Proc. UNITECR ’95, Kyoto,
Japan, 1995, Technical Association of Refractories Japan,
321–328.
International Materials Reviews 2001 Vol. 46 No. 3
166 Lee et al. Castable refractory concretes
76. . , . , . , and . : Proc.
UNITECR ’97, New Orleans, LA, 1997, American Ceramic
Society, 1315–1323.
77. . . , . . , and . . . : Adv.
Ceram., 1984, 13, 131–135.
78. . , . -, and . : in
‘Calcium aluminate cements’, (ed. R. J. Mangabhai), 65–80;
1990, London, E. & F. N. Spon.
79. . , . , . , and . : Adv.
Ceram., 1984, 13, 201–210.
80. . .  and . . : Proc. UNITECR ’99, Berlin,
Germany, 1999, German Refractories Association, 81–85.
81. . . , . , and . . : Interceram,
1982, 31, (5), 519–523.
82. . . -, . . , and . . : ‘Calcium
aluminate cements 2001’, 491–501; 2001, London, IoM
Communications.
83. . , . , . , and . : Proc.
UNITECR ’99, Berlin, Germany, 1999, German Refractories
Association, 86–89.
84. .  and . . : Proc. ALAFAR 25, Bariloche,
Argentina, 1996, 33–42.
85. . . , . , and . : Proc. ALAFAR 25,
Bariloche, Argentina, 1996, 21–29.
86. .  and . . : Proc. UNITECR ’97, New
Orleans, LA, 1997, American Ceramic Society, 43–52.
87. . , . , and . . : Proc. UNITECR ’95,
Kyoto, Japan, 1995, Technical Association of Refractories
Japan, 173–180.
88. . . , . , . , and . : Proc.
UNITECR ’95, Kyoto, Japan, 1995, Technical Association of
Refractories Japan, 357–364.
89. . , . , and . : Proc. UNITECR ’97, New
Orleans, LA, 1997, American Ceramic Society, 1347–1354.
90. . , . , and . : J. Eur. Ceram. Soc.,
1999, 19, 1575–1583.
91. . : Proc. Symp. ‘Chemical cements’, Stockholm, 1938:
Ceram. Abstr., 1940, 19, (7), 154.
92. . .  and . : Can. J. Res., 1941,
19B, 123–128.
93. . .  and . : J. Am. Ceram. Soc., 1956, 39,
(12), 434–442.
94. . : in ‘Refractory concrete’, 105–150; 1978, Detroit,
American Concrete Institute.
95. . . : ‘The microstructure of refractory calcium
aluminate cements’, PhD thesis, University of Sheffield, 1983.
96. . , . , . , . , . .
, and . : J. Am. Ceram. Soc., 2000, 83,
2481–2490.
97. . .  and . . : in ‘Ceramic processing before
firing’, 277; 1978, New York, Wiley.
98. . , . , and . . : J. Eur. Ceram. Soc., 1998,
18, 813–820.
99. . ac: in ‘Alumina chemicals – science and technology
handbook’, 109–170; 1990, Westerville, OH, The American
Ceramic Society.
100. . ac, . . , and . . : Adv. Ceram., 1984,
13, 285–301.
101. . .  and . : Proc. UNITECR ’95, Kyoto, Japan,
1995, Technical Association of Refractories Japan, 223–227.
102. . . : ‘Principles of ceramics processing’, 2nd edn; 1995,
New York, Wiley.
103. . , . , . , and . : Adv.
Ceram., 1984, 13, 245–256.
104. . .  and . . : Proc. UNITECR ’95, Kyoto,
Japan, 1995, Technical Association of Refractories Japan,
351–356.
105. . , . , . , and . : Proc. UNITECR
’97, New Orleans, LA, 1997, American Ceramic Society, 81–90.
106. . , . , and . : Proc. UNITECR ’97,
New Orleans, LA, 1997, American Ceramic Society, 613–624.
107. . , . , and . : T aikabutsu Overseas,
1982, 2, (2), 55–60.
108. . . , . . , and . . : Am. Ceram. Soc.
Bull., 1997, 76, (3), 87–91.
109. . , . , and . : T aikabutsu
Overseas, 1989, 9, (1), 41–53.
110. . . , . , . . , and . . :
Bull. Am. Ceram. Soc., 1998, 77, (12), 60–66.
International Materials Reviews 2001 Vol. 46 No. 3
111. . . , . , . , and . :
T aikabutsu Overseas, 1990, 10, (1), 35–37.
112. .  and . : Indian Refractories Congr.,
Jamshedpur, India, 1994.
113. . : 23rd ALAFAR Congr., Puerto Vallarta, Mexico,
November, 1994.
114. . . , . . , . VAN , . ,
and . VAN DER : Proc. UNITECR ’97, New Orleans,
LA, 1997, American Ceramic Society, 645–655.
115. . . , . , . . , . ,
. , and . VAN DER : Proc. 39th Int. Colloq.
on ‘Refractories’, Aachen, Germany, 1996, 211–218.
116. . : American Ceramic Society 30th Annual Refractory
Symp., St. Louis, MS, March 1994.
117. .  and . : ‘Tabular alumina based refractory
castables – Part 1: The effect of microsilica additions on flow
and cold strength of tabular alumina based low and ultralow
cement castables’, Tech. Rep., Elkem.
118. . , . , and . : Proc. UNITECR ’99,
Berlin, Germany, German Refractories Association, 1999,
26–30.
119. .  and . : ‘Tabular alumina based refractory
castables – Part 3: Reactions in the bond phase of microsilica
containing refractory castables’, Tech. Rep., Elkem.
120. .  and . : ‘Tabular alumina based refractory
castables – Part 2: Hot strength of microsilica-containing
tabular alumina castables’, Tech, Rep., Elkem.
121. . : Br. Ceram. T rans. J., 1991, 90, 149–152.
122. . .  and . : Proc. UNITECR ’97, New
Orleans, LA, 1997, American Ceramic Society, 91–100.
123. . . : in ‘Alumina chemicals – science and technology
handbook’, 99–108; 1990, Westerville, OH, American
Ceramic Society.
124. . . , . . , . . , and . . : Proc.
UNITECR ’97, New Orleans, LA, 1997, American Ceramic
Society, 583–592.
125. . . c, . . , and . . : Proc.
28th ALAFAR (Latin American Society of Refractory
Manufacturers) Congr., Margarita, Venezuela, 1999, 1–13.
126. .  and . . : Int. Mater. Rev., 2000, 45, (2), 41–58.
127. . , . , . . , and . . : J. Am.
Ceram. Soc., 2001, 84, (2) 426–434.
128. . . , . . . . , and . . : Proc.
UNITECR ’95, Kyoto, Japan, 1995, Technical Association of
Refractories Japan, 337–345.
129. . , . , and . : Proc. UNITECR ’95,
Kyoto, Japan, 1995, Technical Association of Refractories
Japan, 237–244.
130. . , . . , and . : Adv. Ceram., 1984,
13, 211–218.
131. .  and . : Veitsch-Radex Rundsch., 1996,
(1), 44–52.
132. . . , . , and . . : Bull. Am.
Ceram. Soc., 1999, 78, (5), 65–72.
133. . .  and . . : Bull. Am. Ceram. Soc.,
2000, 79, (10), 53–59.
134. . . , . , . . , . , and
. . : Bull. Am. Ceram. Soc., 2000, 79, (2),
49–55, 84.
135. . . , . . , . . , and . .
: Proc. Int. Symp. on ‘Advances in refractories for
the metallurgical industries II’, Montréal, Québec, 1996,
209–220.
136. . . , . , . , . , and . :
Proc. UNITECR ’97, New Orleans, LA, 1997, American
Ceramic Society, 593–602.
137. . . : Proc. Int. Symp. on ‘Advances in refractories
for the metallurgical industries II’, Montréal, Québec, 1996,
221–232.
138. . . : Proc. Int. Symp. on ‘Advances in refractories
for the metallurgical industries II’, Montréal, Québec, 1996,
233–244.
139. . . , . . , and . . : Bull. Am. Ceram. Soc.,
1963, 42, (9), 486–489.
140. . . , . , . , and . : Refract. Appl.,
November 2000, 3–4.
141. . , . , . . , and . . :
Bull. Am. Ceram. Soc., 2000, 79, (12), 65–69.
142. . . , . , . , and . : Proc. UNITECR
’97, New Orleans, LA, 1997, American Ceramic Society, 15–21.

143. . . , . . , and . . : Proc. UNITECR
’97, New Orleans, LA, 1997, American Ceramic Society,
1575–1580.
144. . , . , and . : Proc. Int. Symp. on
‘Advances in refractories for the metallurgical industries II’,
Montréal, Québec, 1996, 257–268.
145. . . : Ogneupory, 1963, 8, 341–347 (English
translation).
Lee et al. Castable refractory concretes 167
146. . , . . , . , and . . : Proc.
44th Int. Colloq. on ‘Refractories’, Aachen, Germany, 2001.
147. . : Proc. 13th Conf. on ‘Refractories’, Prague, Czech
Republic, 2000, Czech Silicate Society, 179–183.
148. .  and . : Proc. UNITECR ’99, Berlin, Germany,
1999, German Refractories Association, 97–101.
149. .  and . . : Br. Ceram. T rans., 2001 (to be
published).
International Materials Reviews 2001 Vol. 46 No. 3