4.

12
Refractories
W. E. LEE
University of Sheffield, UK

4.12.1 INTRODUCTION 1
4.12.1.1 Refractory Types and Production Routes 1
4.12.1.2 Refractories as Composite Materials 3
4.12.1.3 Property Requirements 4
4.12.2 MANUFACTURE OF SHAPED (BRICK) AND UNSHAPED (MONOLITHIC) REFRACTORIES 5
4.12.2.1 Aggregate and Bond Production Techniques 5
4.12.2.2 Powder Packing 6
4.12.2.3 Brick Shape Forming and Monolithic Installation 6
4.12.2.4 Drying 7
4.12.2.5 Microstructure Development 8
4.12.3 LOW THERMAL MASS REFRACTORIES 11
4.12.3.1 Fibers for Thermal Insulation 11
4.12.3.2 Highly Porous Refractories 13
4.12.3.2.1 Open-cell structures 13
4.12.3.2.2 Closed-cell structures 13
4.12.3.2.3 Property±porosity relations 15
4.12.4 THERMOMECHANICAL PROPERTIES 17
4.12.4.1 Strength and Toughness 17
4.12.4.1.1 Basic strength tests 17
4.12.4.1.2 Work of fracture 17
4.12.4.1.3 Toughness 18
4.12.4.1.4 Refractoriness under load (RuL) 19
4.12.4.2 Thermal Expansion and Thermal Conductivity 19
4.12.4.3 Thermal Shock Resistance 20
4.12.4.4 Refractories Failure Mechanisms 22
4.12.5 REFERENCES 23

4.12.1 INTRODUCTION manufacture and microstructure development,

This chapter describes the production, micro-
structures, and properties of refractories.
Refractories are not often thought of as com-
posites which is surprising because frequently
they are made of complex configurations of
several materials, are commercially vital, and
used in massive quantities. An important aspect
of this contribution is to bring refractories to
the attention of the broader composites com-
munity. It is split into four sections, an intro-
duction defining the types of refractories and
their property requirements, a section on their
a description of low thermal mass refractories
including fibers and cellular ceramics, and fi-
nally, a section illustrating typical values of
relevant thermomechanical properties.
4.12.1.1 Refractory Types and Production
Routes
Refractories are materials that are resistant
to high temperature, used predominantly as
furnace linings for elevated temperature
materials processing and other applications in

1
2 Refractories

Figure 1 Schematic microstructures of refractories made from (a) large aggregate and finer matrix powders
and (b) cast, electrofused ceramic.

which thermomechanical properties are critical.
Significant consumers of refractories are the
glass melting, cement, and ceramic industries
each using about 8% of production. However,
by far the greatest user is the iron and steel
industry consuming about 65% of production.
Materials encompassed by this definition range
from relatively dense (up to 90%) bricks to low-
density (10%) fibrous thermal insulation. Re-
fractories may be fabricated and sold shaped
(e.g., as bricks) or unshaped (monolithics or
fibers).
Shaped (brick) manufacture is most often
from powder mixtures commonly combining
many different material types, such as ceramic
(oxide) powders, graphite flakes, and polymer
resins, to form the final product. The powders
have a large size distribution enabling small
(submicrometer) particles to pack in the gaps
between large (up to several mm) particles so
that most of the densification occurs during the
shape-forming operation. This is unlike engi-
neering ceramics where most densification is in
the sintering step. Unfired, powder processed
refractories are often 85% dense. The large (up
to several meters and several tonnes) brick sizes
produced could not accommodate large shrink-
age stresses on firing so the processing route is
designed to avoid them. Such a production
route gives a complicated microstructure,
often with extensive porosity, but which confers
the properties desired (Lee and Rainforth,
1994). Figure 1(a) is an idealized schematic
diagram of the fired microstructure composed
of large, discrete aggregate (filler) refractory
grain particles held together by a continuous
bonding matrix, a so-called grain and bond
microstructure. A common feature of such a
microstructure is microcracking from thermal
expansion mismatch of different phases, and
from sintering of the fine particle fraction caus-
ing shrinkage and opening up of cracks between
the larger particles which do not sinter as
rapidly. If smaller than the critical flaw size
such microcracks provide useful toughening,
increasing resistance to crack propagation and
 Introduction
improving thermal shock resistance (Section
4.12.4.3).
Refractory blocks are also made from molten
liquids produced in electric arc furnaces that are
poured into graphite molds and cooled slowly
over several days. Such a process gives a micro-
structure much like a cast metal as shown in
Figure 1(b) for these fused cast (electrocast or
electrofused) refractories. Crystallization from
the melt and subsequent grain growth leads to
interlocked grains that may be up to several mm
long. Low levels of porosity and little glassy
phase may result from this route so that fused
blocks are used in applications where extreme
chemical resistance is required since slag/melt
ingress is limited by such a microstructure.
Unshaped material can be installed and
shaped in situ. Such monolithics include ca-
stables (sold as dry mix which, when mixed
with water, can be shaped by casting or vibrat-
ing, the hydraulic cement chemical bond forms
at room temperature and converts to a physical
ceramic bond on firing), as gunning mixes
(flowing mixtures specially made for placing
by pneumatic or mechanical projection), or as
moldables or plastics (in a plastic ªclayº form
which can be rammed into position and fired in
situ to give a ceramic bond although these are
less popular as their installation cannot be ea-
sily mechanized). Once installed and fired the
microstructures of monolithic refractories are
much like those in Figure 1(a) although poros-
ity levels in the bond may be higher than in fired
bricks. Refractories are also made in lump or
ground form (aggregate/grain) or as fiber wool
and shapes (such as mats and felts). Highly
porous (530% dense) refractories such as
fiber shapes are termed low thermal mass
(LTM; see Section 4.12.3). Unshaped mono-
lithic and LTM materials account for over
50% of refractories usage.
LTM refractories are used most often for
thermal insulation. Providing thermal protec-
tion for a high-temperature furnace usually
involves several layers of refractory. The
inner, contact, or wear lining is exposed to the
highest temperature and is in direct contact
with the furnace contents, e.g., molten metal,
slag, glass, corrosive gases, and fluidized parti-
cles. The inner lining must, therefore, be resis-
tant to chemical and erosive attack and,
consequently, it is the best quality refractory
with the lowest porosity. Its high density does
not usually provide adequate thermal insula-
tion that instead is provided by a separate,
porous, outer layer of refractory in brick, pow-
der, or fiber form (the LTM refractory). This
second layer is also the safety lining that pro-
vides back-up in case of failure of the contact
layer.
3
LTM refractories have three major advan-
tages in furnace linings. First, the air space in
the pores confers low thermal conductivity so
that heat is retained in the furnace. Second, low
thermal mass means that less fuel is required to
heat to temperature than with heavy bricks that
have to be heated themselves. Finally, their
light weight makes installation easy. Ther-
mally-insulating bricks can be manufactured
from aluminosilicates such as fireclays with
high porosity (60±85%). This is achieved by
mixing sawdust or polystyrene into the powder
batch that is fugitive, burning out on firing to
leave residual porosity. Alternatively, foaming
agents may be added to a powder slurry mix
which produce a lightweight structure during
casting and setting, or natural lightweight ag-
gregates such as vermiculite or diatomite may
be used. Such bricks have low strength and slag
resistance due to the large ªflawsº and high
surface area but are ideal for thermal insula-
tion.
LTM refractories are also used commonly to
filter out particulates from fluids passed
through them such as in molten metal and
diesel engine exhaust filters. Foamed or reticu-
lated structures are used in these applications
and are produced in a variety of ways (Section
4.12.3.2). The earliest route developed involves
coating and recoating a reticulate polymer
sponge with a ceramic slurry and firing to
remove the polymer and sinter the ceramic
skeleton (Schwartzwalder and Somers, 1963).
4.12.1.2 Refractories as Composite Materials
Fired brick or monolithic refractories invari-
ably contain many phases, each of which pro-
vides useful properties or has enabled the
processing to be performed. The aggregate/
grain phases in different systems do not vary
much, commonly being fused or sintered Al2O3,
MgO, and spinel (MgCr2O4, MgAl2O4). Where
these refractories do differ is in the bonding
systems used that include ceramic, cement,
and carbon types. These may, e.g., be ceramic
bonds derived from clay which on firing leaves
mullite and an aluminosilicate glass or from
fine additions of Al2O3, MgO, and SiO2 react-
ing to form mullite, spinel, and glass. In mono-
lithics, where castable or gunning slurry is
installed which must then set or harden and
dry, hydratable cement bonds, typically based
on calcium aluminate cements, are used. These
undergo hydration reactions forming, e.g.,
CAH10 and C2AH8 (the cement shorthand
is used where C = CaO, A = Al2O3 and
H = H2O; subscripts indicate number of
4 Refractories
moles) on mixing with water which lead to
setting after installation and then react at high
temperature to give a ceramic bond (see Chap-
ter 4.11, this volume). Carbon bonds derived
from pyrolysis of pitch or phenolic resin binders
form in oxide±carbon refractory bricks used
extensively in primary steelmaking operations.
Thus all three, i.e., ceramic, cement, and carbon
bond (matrix) systems given in the title of this
volume occur in refractories and each will be
discussed in the ensuing sections.
These materials are true composites in that
each constituent contributes useful behavior to
the system. For example, in oxide±carbon re-
fractories the oxide confers oxidation resistance
and refractoriness while the graphite provides
increased thermal conductivity, nonwetting be-
havior (to hot metal and slag), and slag resis-
tance. Since oxide and graphite would react at
high temperatures a third phase is required to
bond them; this is the carbon derived from the
pitch or resin. The softening of the resin or
pitch at relatively low temperatures enables
the batch to flow facilitating shape forming.
Once shaped pyrolysis of the binder leaves
fine carbon that also has the beneficial proper-
ties of graphite listed above. As another exam-
ple, the clay used in ceramic bonded refractories
enables control of the rheology and shaping
operations even though the aluminosilicate
glass resulting from its decomposition degrades
high temperature properties. Similarly, the ce-
ment bond in castable and gunning monolithics
enables these installation procedures to be per-
formed before hydration is encouraged (Section
4.12.2.3).
Often metal is added to refractories such as
stainless steel fibers in monolithics which im-
prove thermal shock resistance by acting as
crack arresters, or Si or Al powder added to
MgO±C bricks to improve oxidation resistance
and high temperature strength. In LTM refrac-
tories it is the porosity which confers useful
properties such as permeability or low thermal
conductivity and can be considered a vital part
of the composite structure (Section 4.12.3.2.3).
4.12.1.3 Property Requirements
Thermomechanical properties are the most
important for refractories and these are quoted
extensively in company literature and publica-
tions. However, the necessarily conservative
nature of the refractories industry means that
many older techniques, such as room tempera-
ture cold crushing strength (CCS) and three-
point bend modulus of rupture (MoR), are still
widely used (Section 4.12.4.1.1). Even though
the information gained from such tests may not
give much scientific insight into the behavior
being measured they are believed useful for
comparative purposes. Clearly, measurement
of properties under service conditions (tem-
perature and environment) is likely to be more
useful (Section 4.12.4) and improved testing
procedures are needed.
The properties of refractories are controlled
carefully to fit the application but retention of
useful behavior to high temperature is invari-
ably desired. Thermal expansion and conduc-
tivity (Section 4.12.4.2) are critical. Usually
refractories are designed to have low thermal
conductivity so heat is retained in the furnace.
This requires controlled levels of porosity (since
air is a poor conductor of heat) but without
excessive loss of mechanical properties or per-
meability by corrosive fluids so that a compro-
mise is reached by which a suitable service life is
achieved before failure and the need for repla-
cement. An alternative approach is to use ma-
terials with high thermal conductivity and
utilize water or air cooling systems to control
the furnace temperature. This is the case, e.g., in
the lower regions of iron blast furnaces that use
predominantly carbon refractories. Levels of
thermal expansion must also be well known
and allowed for in furnace construction. 0.1%
expansion of a 50 m long structure means that
5 cm gaps must be built into it to close during
heat up. Spectacular failures can result from
miscalculation.
Mechanical properties such as strength and
toughness (Section 4.12.4.1) must be adequate
at room temperature for handling and installa-
tion and ideally better at high temperature.
Compressive strength is particularly important
in the lower brick courses of massive structures
such as blast furnaces and glass tanks. Addi-
tives may be made on processing which im-
prove high temperature properties. For
example, metals such as Si, Mg, and Al are
added to MgO±C bricks for primary steelmak-
ing vessels to react in service and form ceramic
bond phases such as forsterite Mg2SiO4, SiC,
and MgAl2O4 spinel which improve high tem-
perature strength (Yamaguchi, 1984).
Refractories also need to withstand changes
in temperature without failure. Thermal shock
resistance (Section 4.12.4.3) is improved by
high thermal conductivity and toughness. In-
corporation of graphite flakes into oxide±C
refractories helps both of these simultaneously
since graphite has high thermal conductivity
and the flakes toughen the microstructure by
crack deflexion, branching and pullout me-
chanisms (Cooper, 1987). Refractories often
fail in service due to physical or chemical at-
tack. Physical attack includes mechanical abra-
 Manufacture of Shaped (Brick) and Unshaped (Monolithic) Refractories
Figure 2 Microstructures of (a) tabular and (b) fused alumina grain. The closed porosity in (a) is believed
to improve toughness by arresting cracks.
sion from ore or scrap burden being loaded or
erosion from dust-laden gases. Chemical corro-
sion consists of fluid penetration and subse-
quent solid dissolution on interaction with the
fluid (Lee and Zhang, 1999). Desirable proper-
ties to maximize lifetimes with respect to such
attack will be considered in Section 4.12.4.4.
LTM refractories are lightweight and the care-
ful balance needed between permeability,
strength, toughness, thermal conductivity, and
porosity will be examined in Section 4.12.3.2.3.
4.12.2 MANUFACTURE OF SHAPED
(BRICK) AND UNSHAPED
(MONOLITHIC) REFRACTORIES
4.12.2.1 Aggregate and Bond Production
Techniques
The microstructure of a typical refractory
made by powder processing consists of a grain
and bond phases. Each of these will have under-
gone extensive synthesis before being incorpo-
rated into a brick. Typical grain materials
include those made by melting or fusion (alu-
mina, mullite, MgO, mullite/zirconia) and sin-
tering (MgO, alumina, Mg aluminate spinel).
Refractory grain may also be derived from raw
materials which have undergone less synthesis
such as fireclays, flint clays, quartz, dolomite,
graphite, bauxite, magnesite, and members of
the andalucite/kyanite/sillimanite group. These
materials may have had relatively simple pre-
5
processing after mining and beneficiation such
as washing and calcination.
Tabular grade alumina is often >99% pure
with controlled particle size and shape
(Figure 2(a)). Tabular alumina crystals are pro-
duced by heating 2 cm diameter pellets of cal-
cined alumina at temperatures >1925 8C, just
below the melting temperature, until near 100%
conversion of the fine, a-alumina crystallites
into large (40 to >200 mm), hexagonal, elon-
gated tablet-shaped crystals occurs. Tabular
alumina crystals are hard and dense with
good thermal conductivity (40 W m71 K71 at
room temperature) and high crushing strength
(30±60 MPa). However, they contain substan-
tial closed porosity due to the large grain
growth leaving pores in the center of grains
where volume diffusion is slow. Tabular alumi-
nas are used extensively in alumina-graphite
refractories, and in low-cement and ultralow-
cement castable mixes.
Fused alumina is produced in two forms:
white and brown. White fused alumina
(Figure 2(b)) is made from calcined Bayer alu-
mina and different grades are available based
on differences in alkali contents. It is used
extensively in high-temperature refractory
bricks and monolithics. Brown fused alumina
is made from bauxite ore under conditions that
allow the partial removal of impurities as fer-
rosilicon. The impurities left lower its melting
temperature by about 50 8C and it is used com-
monly, e.g., in refractories for blast furnace
trough and induction furnace linings. MgO is
6 Refractories
available from magnesite (MgCO3) ore or de-
rived from sea water. Hydration resistance is
improved by dead burning or liquid phase sin-
tering the fine MgO with, e.g., CaO, Fe2O3, and
SiO2 to encourage grain growth and aggregate
formation leaving less surface area available for
reaction with moisture. Common second
phases in dead-burned magnesias are dicalcium
silicate and forsterite. SiC is synthesized com-
mercially in large quantities via the Acheson
process utilizing a batch of coke and sand. A
mound of the batch is resistively heated to
2200 8C between C electrodes causing the
exothermic reaction C and SiO2 to give SiC
and CO gas. The mound is cooled and broken
up to reveal large pure SiC single crystals in the
center and lower purity SiC grains towards the
outside.
Production of bond phase constituents typi-
cally involves more processing than that of
grain phases since the particle sizes are finer,
often submicrometer. Aluminosilicate refrac-
tories to be used at low temperatures
(51000 8C) such as firebricks contain bond
phases derived from reaction of clays with fine
alumina to give a mullite±glass bond (Rezaie
et al., 1997). The carbon bond in oxide±C
bricks is derived from a phenolic resin or
pitch added as a binder during shape forming
(Rand and McEnaney, 1985). Decomposition
of the pitch or resin leaves a fine, reactive
carbon bond. The most common bond system
in monolithic castables is based on calcium
aluminate cements (CACs) often with addi-
tional calcined Bayer (reactive) alumina and
silica. CACs are formed by reaction of lime
and alumina either by a sintering or clinker
process or from fusion (Kopanda and Mac-
Zura, 1990). The cements are predominantly
CA and CA2 although minor C12 A7 may be
present. Several grades of calcined Bayer pro-
cess (in which Al(OH)3 gibbsite is precipitated
from dissolved bauxite ore) alumina are avail-
able. The level of soda impurity is critical since
it leads to formation of Na b-alumina
(Na2O.11Al2O3) on sintering that causes re-
duced density, strength, thermal shock, and
corrosion resistance.
4.12.2.2 Powder Packing
The raw materials are beneficiated, ground,
and classified into particle size fractions
commonly defined as coarse (>1.2 mm), inter-
mediate (0.25±1.2 mm), and fine (50.25 mm).
Unlike in other engineering ceramics almost all
of the densification of refractories occurs before
firing so that this step must be controlled care-
fully. The correct proportion of each fraction is
required in the batch to give the required prop-
erties in the end product. Furnas (1931) devel-
oped mathematical expressions for the grading
(or particle size distribution, i.e., proportion of
discrete, often bimodal size fractions) which
would give maximum density packing in a pow-
der. The pore volume in a packed powder is a
function of the proportion of each size fraction
present and the ratio of the finest to coarsest
particle size. This is significant in that fine
particles can fill the space between coarse
ones. Two important rules of thumb for bimo-
dal size distributions are that a 7:1 ratio of
coarse particle to fine particle size and a 70:30
ratio of coarse to fine particles gives optimum
packing. In general, these rules also apply to
continuous distributions of particle sizes. Funk
and Dinger (1994) modified earlier equations to
emphasize the importance of the finest particle
size (Ds), i.e.,
CPFT Dn ÿ Dns
ˆ n …1†
100 Dl ÿ Dns
where CPFT is the cumulative percent finer
than a particular size, D = particle diameter,
Dl = largest and Ds = smallest particle dia-
meter, and n is the distribution modulus. A
typical mix for maximum density is 40%
coarse, 30% intermediate, and 30% fines but
maximum density is not always required in
refractories (e.g., if they are required to be
thermally insulating) in which case, e.g., the
proportion of gap filling fines would be re-
duced. Alternatively, a fugitive phase can be
added which burns out leaving pore space in
the microstructure.
This equation is not only critical when con-
sidering particle packing during shape forming
operations but also for installation of mono-
lithics since particle packing and flow are
strongly coupled. High packing density leads
to controlled rheological behavior, easy instal-
lation, and suitable properties. For example, a
typical vibratable castable has n between 0.28
and 0.30 while to induce self-flowability ca-
stables should have n of 0.25±0.26. This indi-
cates that self-flowing behavior is, at least in
part, achieved by increasing the fines content.
4.12.2.3 Brick Shape Forming and Monolithic
Installation
The correctly sized powder with added binder
is shaped to a brick by pressing, extruding, or
casting into standard shapes. Pressing is done
using biaxial (double pressure) or isostatic, fric-
tion or hydraulic presses. Refractories with a
 Manufacture of Shaped (Brick) and Unshaped (Monolithic) Refractories 7

Figure 3 Schematic diagrams of some monolithic installation procedures: (a) vibration casting, (b) dry
gunning, and (c) wet gunning (or shotcreting).

high percentage of fines such as MgO±carbon
bricks contain a lot of air after normal pressing
so that additional vacuum is applied. The green
(unfired) strength of the bricks is not high and
they will only tolerate gentle handling until
strength has been developed by firing (Section
4.12.2.5).
Control of rheology or flow behavior is
clearly critical for installation of monolithic
refractories that need to be pumped and then
cast or sprayed into place (Figure 3). As well as
particle size packing constraints considered in
the preceding section, particle motion is a com-
plex function of powder shape and surface
chemistry. A range of chemical additives is
used to control the interaction between indivi-
dual particles including coagulants and disper-
sants, setting accelerators, and retarders as well
as water. Water is necessary for the hydration
reactions to set the cement binder system but its
level is generally kept to a minimum since water
removal on drying leads to open pore channels
that degrade mechanical properties and allow
ingress of corrosive fluids. In dry gunning sys-
tems water is mixed with the powder batch at
the nozzle (Figure 3(b)) but this leads to high
levels of rebound and health problems with
dust emissions. In the wet gunning (or shotcret-
ing) process the powder batch and water are
premixed and a coagulant added at the nozzle
(Figure 3(c)). This reduces dust hazard and
rebound levels to almost zero.
4.12.2.4 Drying
Water removal by drying is important since
the moisture escape leaves flaws in the micro-
structure that can adversely affect properties. It
is especially important in monolithic refrac-
tories using hydraulic binder systems. The dry-
ing procedures for gunned and castable
refractories can be long and complex, taking
several days to ensure all moisture escapes. Any
entrapped water will convert to steam and
cause explosive spalling on heating the furnace
to use temperatures. Ideally, the channels
through which the water escapes should close
on firing to give suitable thermomechanical
8 Refractories
Figure 4 Microstructure of a fireclay brick with prefired clay (grog) aggregate held in a clay-derived bond.
Resin-filled cracks (C) arise from clay firing shrinkage.
properties in service. About 0.05% of organic
fibers such as polypropylene (*6 mm long and
*20 mm diameter) may be added to the batch
to aid water escape and reduce drying times for
monolithics. These fibers are burned out and
the resulting gaps closed by sintering on firing
(Section 4.12.2.5) so that property degradation
is minimised.
4.12.2.5 Microstructure Development
Since most densification is done prior to
firing refractories, the purpose of this operation
is bonding together of the phases in the micro-
structure to improve strength. In powder-pro-
cessed refractories the finer, more reactive,
matrix phases react and bond the larger aggre-
gate phases. This leads to strength development
but since many different phases are present it
may also leave high levels of residual stress,
microcracking, and gaps arising from thermal
expansion mismatch. Such behavior is, how-
ever, controlled to give the desired properties
in the final product.
Refractories are often characterized by the
nature of their bond system. In silicate, glass, or
clay-bonded refractories the clay is often added
as a powder, and with other, often alumino-
silicate, phases such as fine alumina, sillimanite,
or andalucite (Al2O3.SiO2) forms the bond. On
firing, clays decompose via dehydration and
dehydroxylation before vitrifying to viscous
melt with various crystalline phases evolving
simultaneously. In kaolinite clays (Al2-
Si2O5(OH)4), after decomposition to metakao-
lin, nm scale g-Al2O3 (with a few % SiO2)
crystals form metastably at about 550 8C
being replaced by mullite and cristobalite at
higher temperature (1200 8C) (McConville
et al., 1998). After firing, the microstructures
of clay-bonded refractories consist of large ag-
gregate/grain phases such as alumina or grog
(prefired aluminosilicate) held together by a
bond containing large shrinkage cracks and
crystalline phases such as mullite or spinel in a
glassy matrix (Figure 4). Softening of the glass
limits the maximum temperature of use.
In carbon-bonded oxide refractories the ag-
gregate phases (typically MgO, Al2O3, or ZrO2)
are held together by a complicated bond system
derived from decomposition of tar/pitch or
phenolic resin binders. While clay-bonded
bricks are fired prior to use C-bonded bricks
are only given a low temperature (3±400 8C)
tempering treatment to stabilize the structure
and remove volatiles before installation. They
are then fired after placement in the use posi-
tion. Various additives may also be made to
them which react in service to give improved
high temperature behavior and oxidation resis-
tance. Microstructural development thus oc-
curs throughout their lifetimes, in contrast to
silicate-bonded refractories where the firing
treatment prior to use is designed to give a
microstructure as close to equilibrium as possi-
ble so that ideally no further change occurs in
service. Two types of additive are used in C-
bonded-MgO refractories (Chan et al., 1998),
 Manufacture of Shaped (Brick) and Unshaped (Monolithic) Refractories 9

Figure 5 Light forsterite layer (F), derived from Si addition, surrounding sintered MgO grain (M) in a
MgO-C brick. The forsterite tightens the texture and helps bond MgO to the carbon phases providing
improved high-temperature properties.

metals/alloys such as Al, Si, Mg, and Ca
(Lubaba et al., 1989) and boron-based com-
pounds such as B, B4C, CaB6, ZrB2,
Mg3B2O6, and SiB6 (e.g., Hayashi et al., 1991;
Hanagiri et al., 1993). These two additive types
work in different ways. Metal/alloy additives
act as CO-reducing agents contributing to car-
bon oxidation inhibition and/or improving hot
strength by forming high-temperature ceramic
bonds such as Mg2SiO4 with Si metal addition
(Figure 5). Boron-based additives, on the other
hand, act to block open pores to reduce the
oxidation of carbon by formation of liquid
phases. This has the drawback of lowering the
hot strength. Carbon-containing refractories
service lives in oxygen-rich atmospheres
depend, to a large extent, on their oxidation
resistance so that these additions have a critical
function.
As well as oxide-grain and carbon-bond
phases, these refractories also contain natural
graphite flakes. The bend strength of graphite-
containing refractories can be low (about
5 MPa with 10% graphite) compared to gra-
phite-free oxides. This is thought to be due to
microcracks (termed Mrozowski cracks) intro-
duced by the graphite which opens up along its
cleavage planes (Cooper, 1987). The smaller the
graphite flake size the higher the strength of the
body due presumably to the smaller defect size.
Bend strength increases with increasing gra-
phite content in a carbon-bonded system
(Figure 6). Bend test measurements of room
temperature strength do not produce a linear
10 Refractories
Figure 6 Influence of graphite content on strength of a fine-textured alumina-graphite refractory (from
Cooper, 1987).
curve (Figure 7). After reaching a maximum
stress the body maintains coherence even as the
strength deteriorates exhibiting ªgracefulº fail-
ure. This behavior, and the increasing strength
with increased graphite content, arises from the
reinforcing effect of the graphite flakes which
essentially act like fiber or platelet reinforcing
phases in CMCs (see Chapter 4.04, this
volume). Figure 8 shows graphite pull-out and
crack branching in a clay-graphite refractory
(Cooper et al., 1985), illustrating that the same
toughening and strengthening mechanisms
operate in these composite systems as in CMCs.
In monolithic refractories evolution of the
bond system is more complicated since a
hydraulic-type bond first forms at, or close to,
room temperature soon after installation by,
e.g., casting or gunning techniques which is
Figure 7 Load±strain curve for a graphite-contain-
ing refractory (after Cooper, 1987).
then fired to give a different high-temperature
bond system. In aluminate-bonded oxide ca-
stable refractories, the fine calcium aluminate
cement powder (containing predominantly CA
and CA2 phases) undergoes setting reactions to
form hydrated phases such as CAH10, C2AH8,
AH3, and C3AH6. The latter two, denser, hy-
drate phases form if hydration occurs above
about 30 8C. While the resulting porosity lowers
the strength of the monolithic it allows water
vapor to escape preventing explosive spalling so
that careful control of the hydration and drying
conditions is needed to give optimum proper-
ties. Firing leads to dehydroxylation to C12A7
above 500 8C with CA and CA2 reappearing
above about 800 8C and eventual formation of
CA6 above about 1200 8C. The CA6 crystals
have a platey morphology, penetrating and
opening up alumina aggregates at high tem-
perature. Powder additions are often made to
the bond system including fine silica, MgO, and
Al2O3. The latter additions lead to formation of
Mg aluminate spinel on firing and in service
(Fuhrer et al., 1998). Spinel formation occurs
between 1200 and 1400 8C with a tuber-like
morphology interlinked with CaO±MgO±
Al2O3±SiO2 (CMAS) phases (Figure 9). The
interlocked CA6 plates and contiguous struc-
ture of the spinel-rich matrix likely contribute
to the good thermal shock resistance of these
refractories since they provide toughening
mechanisms such as crack bridging and deflex-
ion. The presence of free alumina in such spinel-
bonded castables can improve the thermal
shock resistance of the system since the thermal
expansion mismatch between the Al2O3
(9 6 1076/K at 1500 8C) and spinel
(10.2 6 1076/K at 1500 8C) leads to a stress-
state that aids crack closure or generates micro-
cracks.
 Low Thermal Mass Refractories 11

Figure 8 (a) Pull-out and (b) crack branching through a clay/graphite refractory.

4.12.3 LOW THERMAL MASS
REFRACTORIES
4.12.3.1 Fibers for Thermal Insulation
Low thermal mass refractory fibers are made,
e.g., from asbestos, kaowool, slagwool, high
silica glass, pure alumina, and aluminosilicates.
The ªlowº grade aluminosilicate material used
for thermal insulation is made by blowing or
spinning. In blowing, alumina±silica or clay-
based materials are melted and formed into a
stream which is subjected to a blast of high-
temperature gas to form fluffy cotton wool like
fibers about 2.5 cm long and 1±10 mm diameter.
For example, Kaowool is a vitreous aluminosi-
licate fiber containing 43±47 wt.% alumina and
53±57 wt.% silica. The blowing process is diffi-
cult to control giving a wide range of fiber sizes
plus particulate contamination. Higher alu-
mina contents cannot be obtained because of
the high viscosity of high alumina melts making
12 Refractories
Figure 9 Tuber-like morphology of the in situ formed spinel/CMAS phases in a CAC castable. Inset shows
chemical analysis of each phase (after Fuhrer et al., 1998).
fiber blowing impossible. These low-grade fi-
bers are also predominantly amorphous in nat-
ure.
High alumina fibers are used for high tem-
perature applications due to their greater re-
fractoriness. Higher purity and higher alumina
content fibers (ICI Saffil alumina, 3M Nextel
mullite) are made commercially by a sol±gel
route (see Chapter 1.05). Depending on fiber
quality and type they can be used from 850±
1600 8C. Refractory mullite fibers are made by
sol±gel processing of colloidal boehmite and
silica that leads to a precursor which is fired
to form mullite. This route requires a much
lower processing temperature but uses higher
purity and expensive starting materials. Saffil
alumina fiber is made by a sol±gel route from
aluminum chloride and colloidal silica. The
route enables any alumina content to be
obtained in the sol which can be dry spun to
green-gel fibers which are pyrolyzed (fired) to
the polycrystalline ceramic with, e.g., 95 wt.%
alumina and 5 wt.% silica. Using this proces-
sing route the alumina content is not limited by
melt rheology as it is in the blowing process so
the fibers are more refractory. These high-grade
refractory fibers tend to be crystalline. The
properties of Saffil alumina are compared to
those of the traditional fiber in Table 1. Saffil
alumina was developed by ICI in the UK in
1975. Fibers produced by this route are cheap,
inert, and widely used, e.g., as thermal insula-
tion linings in steel heat treatment furnaces
where the low thermal mass means fuel savings
over refractory bricks. Applications are cur-
rently being developed in metal matrix (alumi-
num) composites.
Short insulating fibers may be used in bun-
dles or longer filaments may be mixed with
organic binders and fabricated into felts,
boards, mats, blankets, and complex shapes
often for the outer insulation in heat treatment
furnaces. The felts and blankets may be im-
paled on anchors (which are also used with
monolithic refractories). Vacuum formed fiber
shapes are used widely as combustion cham-
bers, burner cones, heating element holders,
aluminum launders, and tap-out cones (Krietz,
1994). Powder/fiber mixtures often of fine silica
are used in cloths, moldables, bricks, and panels
for applications such as continuous casting
tundish linings, steel ladles, oil refinery liners,
and aircraft black box recorder liners. LTM
refractories and monolithics often are used for
suspended furnace roofs and, in particular, in
slab reheating furnaces that are used intermit-
tently. LTM refractories are used in many com-
mon domestic appliances such as fireplaces,
water heaters, electric stove element holders,
irons, and ironing boards.
The classification of refractory ceramic fibers
as Category II carcinogens and the ensuing
limits on their use as thermal insulation has
encouraged development of suitable alterna-
tives. Traditional clay-based refractory bricks
meet some requirements but their thermal
 Low Thermal Mass Refractories 13

Table 1 Properties of high and low grade refractory fibers.

Property Saffil alumina Kaowool

Crystallinity Polycrystalline Vitreous

Composition 95 wt.% Al2O3, 43±47 wt.% Al2O3,
5 wt.%SiO2 53±57 wt.% SiO2
Density (g cm73) 2.5 2.56
Melting point (8C) 1980 1860
Max. use temp (8C) 1400 1260
Tensile strength (GPa) 1.0 1.4
Young's modulus (GPa) 100 120

shock and insulation properties are often inade- cluding the desired ceramic constituents, are
quate. For these reasons, highly porous refrac- combined to form a foam from evolved gas,
tories as described in Section 4.12.3.2 are and a polymer carrier is burned out leaving a
replacing fiber insulation in many applications. closed, open, or mixed-cell structure.

4.12.3.2.1 Open-cell structures

4.12.3.2 Highly Porous Refractories
In this discussion highly porous refractories
are defined as those with 530% density to
distinguish them from denser bricks and mono-
lithics. Porous refractory ceramics can be
grouped into two general categories consisting
of either open or closed cells. A closed cell
ceramic can be visualized as a network of
soap bubbles, i.e., closed voids within a contin-
uous ceramic matrix (Figure 10(a)). An open
cell (reticulate) structure has the membranes
separating the cells removed and so is com-
prised of continuous, interconnected open
voids surrounded by a web of ceramic
(Figure (10b)). Mixed open/closed cell systems
are possible. Open-cell structures have high
permeability but this property is low in closed
cell ceramics. Both types have relatively low
mass, low density, and low thermal conductiv-
ity. The most common applications for open-
cell porous ceramics are molten metal and die-
sel engine exhaust filters although they are also
used as catalyst supports and industrial hot gas
filters. Both open and closed cell ceramics are
used as light structure plates, thermal-insulat-
ing materials, fire protection materials, and gas
combustion burners. None of these applica-
tions require much load bearing since these
cellular ceramics have low strength and tough-
ness. Typical ceramics used in cellular form
include SiC, vitreous carbon, alumina, and alu-
mina-mullite.
Highly porous refractories are manufactured
using two main techniques (Saggio-Woyansky
et al., 1992). In the polymeric sponge method, a
polymer sponge is impregnated with a ceramic
slurry and then burned out leaving a porous
ceramic typically with open-cell (reticulate)
structure. In the foam method reactants, in-
The steps to fabricate an open cell structure
are shown in the Figure 11. Polyurethane is the
most common sponge material due to its suita-
ble pore size that determines the pore size of the
final product. It also has a low softening tem-
perature allowing relief of thermal stress which
otherwise disrupts the green ceramic and a low
volatilization temperature for easy removal of
organics. Almost any ceramic powder can be
used in the slurry depending on the final appli-
cation usually with particle diameter 545 mm.
Water is the most common carrier. The com-
pressed sponge is immersed in the slurry and
allowed to expand so the slurry fills its open
cells. After removal of excess slurry the infil-
trated sponge is dried, fired at intermediate
temperature (350±800 8C) to pyrolyse the poly-
mer and sintered at a controlled temperature
(1000±1700 8C) sufficient to give densification
but not allow collapse of the ceramic frame-
work. The open cells are usually >1000 mm in
diameter.
The structure of any cellular material consists
of its macrostructure or the arrangement and
configuration of the cells and the particulate
microstructure within the solid cell membrane.
The cellular ceramic contains cells or bubbles,
struts, and windows (Figure 10). In open-cell
structures made by the polymeric sponge
method, the burnout of the polymer leaves the
struts hollow (Figure 12), the central hole being
the original location of the polymer. This por-
osity weakens the material.
4.12.3.2.2 Closed-cell structures
In general, closed-cell structures are made
from a mixture containing the ceramic powder,
14 Refractories

Figure 10 Morphology of (a) closed-cell and (b) open-cell ceramics containing cells (C), struts (S), and
windows (W).

polymeric binders, and water which is treated
to evolve a gas which creates bubbles and
causes foaming. The foamed structure is re-
tained often by gelation and dried and fired as
in the sponge method. Smaller pores
(5700 mm) can be made in this way than in
the sponge method. The cells form as a result of
introducing gas into the ceramic slurry. Where
the cells touch they tend to change shape to
maximize packing density and the slurry drains
from the point of contact towards the strut. The
struts are the building blocks of the cellular
structure and have a critical effect on toughness
and strength (Section 4.12.3.2.3). A thin film of
liquid remains at the region of contact between
cells which leaves the windows after drying and
firing. These connect each cell and can be ma-
nipulated in size by varying, e.g., the amount of
gas introduced. The particulate ceramic micro-
structure within the cell windows and struts can
be sintered to either full density or to be highly
porous. A dense microstructure confers rela-
tively high strength and toughness on the re-
sulting body.
 Low Thermal Mass Refractories
Figure 11 Block diagram of processing route to open cell ceramic via the sponge method.
4.12.3.2.3 Property±porosity relations
The pores (cells) are an important part of the
microstructure in these refractories conferring
useful properties of permeation and thermal
insulation. However, a compromise needs to
be achieved between the desired low weight,
high thermal insulation and permeation, and
the resulting low strength and fracture tough-
ness. Brezny and Green (1994) summarize
recent work on the mechanical behavior of
cellular ceramics. Fracture toughness was
shown by Maiti et al. (1984) to depend on
strut mean bend strength (ss), cell size (L),
and relative density by the relation
p
KIc ˆ Css pL…d=ds †3=2 …2†
where d is foam density, ds is strut density, and
C is a constant. Strut strength has been found
not to be constant, being a function of local
densification and strut volume. Clearly KIc de-
15
pends strongly on the dispersion of strut
strengths. Toughness can increase or decrease
with cell size depending on the volume distribu-
tion of strut strengths.
Zhang and Ashby (1989) describe the bulk
properties of cellular ceramics in terms of in-
dividual strut properties following a relation of
the form foam property/strut property
/(r/rs)3/2. Their model assumes deformation
involving strut bending and strut strength is
described as an intrinsic characteristic of the
solid phase within the foam, related to the
foams compressive strength (sc) by
sc = Css(r/rs)3/2 (3)
where C is a geometrical constant. The equa-
tions for tensile and compressive strength of
cellular materials are of the same form so that
values of compressive and tensile strength are
similar. This is in contrast to dense ceramics in
which compressive strengths are often an order
16 Refractories
Figure 12 Triangular pore in hollow strut left by burnout of the polymer sponge on fabrication of an open
cell ceramic (after Brezny and Green, 1994).
of magnitude greater than tensile strengths.
Highly porous ceramics have relatively low
strength (sc54 MPa) and toughness
(50.5 MPa m1/2 ), particularly those made by
the sponge process since after burn-out this
leaves very thin (510 mm) or nonexistent win-
dows and hollow struts due to the volatilization
of the organic filament substrate (Figure 12). It
is important to realize that cellular ceramics can
contain both macroscopic and microscopic
flaws. Macroscopic flaws are broken cell struts
and other imperfections in the cell structure
whereas microscopic flaws consist of pores or
cracks within the cell struts and windows
(Brezny and Green, 1989). Control of flaw
populations during processing is critical for
achieving reasonable mechanical properties.
While a simple correlation of increased strength
with decreased cell size might be expected
Brezny and Green (1990) show that strut
strength and cell to flaw-size ratio must be
considered and both can vary with cell size.
Adequate strength is particularly important
for filters where the reticulate structure must
withstand thermal shock and resist the high
temperature corrosive environment of hot
metal and gases. One way to improve strength
of highly porous ceramics is by ceramic fiber
addition. Aluminosilicate fibers were used by
Washbourne (1976) in lithium aluminosilicate
and Blome (1981) in alumina-chromia cellular
ceramics. Other strengthening techniques in-
clude use of attacking agents such as mono-
ethylene glycol and stearic acid to partially
remove the sponge prior to burn out (Ravault,
1974). The lower polymer volume enables bet-
ter ceramic packing, more coherent structure
and improved strength. Hargus et al. (1989)
describe a strengthening method in which the
sponge is sprayed with an adhesive and treated
with organic fibers prior to immersion in the
slurry. The adhesive improves the wetting of the
sponge by the slurry and the fibers cause slurry
particles to flocculate. Together these produce a
thicker coating with more uniform coverage
and greater strength.
Ideally, a filter should be able to remove the
maximum of impurities with a minimum of
resistance to flow. The latter can be achieved
by increasing either the void volume (porosity)
or the fluid passage (pore size) within the struc-
ture. Both options decrease strength. Optimiz-
ing the permeability/strength relation depends
on an ideal combination of pore (cell) diameter
(d) and total pore volume (V). Ceramic foams
exhibit a relation of the form (Gibson and
Ashby, 1996)
1 7 V = C(t/d)2 (4)
where t is the strut thickness and C is a con-
stant. Increased mechanical strength through
reduced porosity is associated with pore size
and permeability reduction. Modern techniques
of foam production allow close control of por-
osity level and size enabling optimisation of
filter properties.
Collishaw and Evans (1994) examined ex-
pressions for the apparent thermal conductivity
of cellular materials considering conductive and
radiative mechanisms since convective contri-
butions are believed negligible for cell sizes
54 mm. Radiation contributes 6±26% of the
 Thermomechanical Properties
apparent conductivity depending inversely on
the solids content.
In many applications such as molten metal
filters cellular ceramics encounter severe ther-
mal stresses. Orenstein and Green (1992) found
that thermal shock resistance of open cell cera-
mic foams was strongly dependent on cell size,
increasing with increasing cell size, and weakly
dependent on density, increasing with increased
density. Sources of thermal stress found to be
significant included temperature gradients
across the struts and the heating by the quench-
ing liquid as it infiltrated the cellular structure.
4.12.4 THERMOMECHANICAL
PROPERTIES
The mechanical properties of refractories of
main interest are those at use (high) tempera-
ture so that the thermomechanical response
needs to be understood. In this section techni-
ques for measuring thermomechanical proper-
ties of refractories will be described. While the
values obtained may appear low compared to
dense, polycrystalline ceramics, they are suffi-
cient for the desired applications and other
commercial factors also must be considered
such as manufacture at low cost and in large
volumes. Nonetheless, improved testing meth-
ods are needed as well as better interpretation
of results in terms of failure mechanisms.
4.12.4.1 Strength and Toughness
In dense, polycrystalline ceramics and CMCs
the minimization of flaw sizes and populations
by processing is critical to give high strength.
However, in refractories the presence of large
populations of flaws (pores) may be desirable to
enhance other properties (low weight, thermal
insulation) so that a compromise between these
properties and strength must be reached.
Achieving maximum strength is rarely the aim
of the refractories engineer.
4.12.4.1.1 Basic strength tests
Much effort has been made globally to stan-
dardize refractories testing. In the following
sections where possible the International Stan-
dards Organisation (ISO) number of the rele-
vant test will be given. The simple Cold
Crushing Strength (CCS) test (ISO 8895-86) is
used widely even though refractories rarely fail
in service by crushing at room temperature.
This test, however, is an indirect quality control
checkÐsamples failing this may, e.g., have been
17
inadequately fired or have poor abrasion resis-
tance. The test piece is a 50 mm diameter cylin-
der or a 75 mm cube and is subjected to
increasing uniaxial compressive load to failure.
The failure mechanism is by shear not compres-
sion and samples show an apple-core shape
after failure. The crushing strength is calculated
from the maximum load indicated at failure
and the mean cross-sectional area over which
the load is applied. Typical room temperature
values of CCS are given in Table 2.
In the simple Modulus of Rupture (MoR)
test the failure of a 150 6 25 6 25 mm rectan-
gular bar is measured in three-point bending.
Measurements can be made at room tempera-
ture (ISO 5014-86) but also more usefully at
high temperature (ISO 5013-85). The MoR ss is
then calculated from
3Fmax l
ss ˆ …5†
2bh2
where Fmax is the load at failure, l is the length
of loaded region, b is the bar breadth, and h is
the bar height. Three-point bending only tests a
small volume of material under the top load
point to maximum stress and four-point bend-
ing, which tests a greater volume of material, is
now the technique most widely used for
strength measurements of ceramics (Wacht-
man, 1996). However, three-point tests do en-
able comparison between groups of refractories
and they are still used extensively by the refrac-
tories industry. Typical three-point hot MoR
values are given in Table 3.
4.12.4.1.2 Work of fracture
The MoR and CCS tests reveal nothing
about the fracture process itself because frac-
ture is the propagation of a crack through a
specimen and these tests do not monitor that
process. Nakayama (1964) devised a chevron
notch test using a precracked specimen and a
stiff testing machine to monitor growth of a
controlled single crack in three- or four-point
bending. Load±deflection curves illustrating
catastrophic, semistable, and stable fracture
are shown in Figure 13. The total work done
is the area under the curve. Integrating the area
under the load-displacement curve gives an
energy term which can be divided by fracture
surface area A to yield a fracture surface energy
which is defined as the work of fracture (g)
Fmax dx
gˆ …6†
2A
(2A as two new surfaces are created, x = dis-
placement).
18 Refractories

Table 2 Room temperature crushing strengths of Table 3 High-temperature bend strengths of re-
refractories. presentative refractories.

CCS Refractory brick MoR

Brick type (MPa) (test temp. 8C) (MPa)

Insulating or foamed 510 Magnesia, C/S =2 (1300) 14

Plastic firebrick 10±30
Sillimanite 30±60
Fused silica 20±30
Silicate-bonded MgO 35±70
Spinel-bonded mag-chrome 30±60
Tempered oxide-graphite 70±90
High alumina 50±100
SiC >200
This test gives a measure of the resistance of
the refractory to crack propagation. For refrac-
tories to have good thermal shock resistance
semistable or stable crack propagation is re-
quired. Typical g values and other mechanical
properties at room temperature are given for
some refractories in Table 4. The successful
development of the work of fracture test for
refractories led to its application to other struc-
tural ceramics and the evolution of other frac-
ture mechanics tests to determine, e.g., stress
intensity factors (KIc) in dense polycrystalline
ceramics. Much current research into mechan-
ical properties of refractories concerns rising R-
curve behavior where there is increased crack
growth resistance as the crack grows (Hender-
son et al., 1997; see Chapters 4.04 and 4.05, this
volume).
4.12.4.1.3 Toughness
Toughening mechanisms in ceramics (see
Chapter 4.04, this volume) can be divided into
100% Alumina (1300) 9
Bauxite (1650) 6
Chrome-mag (1260) 14
(1500) 6
Mullite (1400) 17
MgO±C(1000) 6
three types (Lutz et al., 1991). (i) Crack deflex-
ion and branching, (ii) contact shielding, or
wedging processes such as those that arise
from bridging and rough crack surfaces, and
(iii) stress-induced zone shielding arising from
transformation toughening, microcracking,
and residual stresses. All of these may operate
in refractories systems. The toughness of refrac-
tories is never directly quoted on manufac-
turers' data sheets but ªtoughº refractories
with high g values have good thermal shock
resistance since crack propagation is then diffi-
cult. Chandler et al., (1997) have developed a
double cantilever beam test specifically to mea-
sure the toughness of refractories.
Refractories have traditionally been tough-
ened by microstructural design. Phases such
as graphite flakes in oxide±C systems (Cooper
et al., 1985) and steel fibers in castables, which
are likely to be bonded weakly to the matrix,
confer toughness by crack bridging, branching,
and pull-out mechanisms (Figure 8). Even large
aggregate phases in conventional powder-pro-
cessed refractories (Figure 4) provide crack de-
flexion. Rising R-curve behavior has been

Figure 13 Typical load±displacement curves illustrating (a) catastrophic, (b) semistable, and (c) stable crack
propagation.
 Thermomechanical Properties
Table 4 Room temperature strength, stiffness, and work of fracture of repre-
sentative refractories.
Refractory
Fireclay
High-fired superduty firebrick
70% alumina
High alumina castable
a
Young's moduli (E) for refractories are obtained using a nondestructive sonic technique.
observed in MgO±MgAl2O4 spinel refractories
arising from release of residual stress by micro-
cracking (Henderson et al., 1997). Unsurpris-
ingly, similar toughening mechanisms occur in
refractories as in CMCs, especially in graphite-
containing systems. The application of flake or
fiber reinforcing phases to improve refractories
toughness and thermal shock resistance is an
area ripe for further research.
4.12.4.1.4 Refractoriness under load (RuL)
RuL is the deformation behavior of a refrac-
tory subjected to the combined effects of load,
time and temperature. Typically, the test entails
applying a compressive load at elevated tem-
perature to determine the resistance of the re-
fractories to deformation (ISO 1893-89). There
are two types of RuL test. In the Rising Tem-
perature Test the specimen under a stress of
0.2 MPa is usually heated at 5±10 8C min71
either until collapse or until a specified amount
of deformation (often 0.5%) occurs. Results of
this test for a range of refractories are given in
Figure 14. Note that silica retains its strength
up to close to its fusion point before sudden
failure whereas fireclay softens over a large
temperature range.
In the Maintained Temperature (Creep) Test
(ISO 3187-89) the specimen under 0.2 MPa
stress is heated at 10 K min71 to a predeter-
mined temperature which is maintained either
for a specified time or until collapse (or pre-
determined deformation) occurs. Results for
several refractories are shown in Figure 15.
Even though the MgO brick (Figure 15(d))
expands most on heating, it has the lowest
dimensional change at temperature.
4.12.4.2 Thermal Expansion and Thermal
Conductivity
As discussed in Section 4.12.1.3 it is impor-
tant that the thermal properties of refractories,
in particular expansion and conductivity, are
19
MoR E g
(MPa) (GPa)a (J m72 )
6 18.6 60
32 69.8 15
10 10.5 75
10 50.1 53
well defined. Thermal expansion is measured
for refractories using a dilatometer configured
for brick size test pieces and typical responses
are given in Figure 16. A related measurement
commonly made on refractories is the Perma-
nent Linear Change (PLC) or Permanent
Volume Change (PVC) test. A
50 6 50 6 60 mm test piece is heated at
5 K min71 in oxidizing atmosphere to high tem-
perature and cooled and the linear or volume
change on cooling measured (ISO 2477-87).
This is believed to indicate how well a refrac-
tory brick has been fired and is a measure of the
change that will occur when the brick is in
service. Values of PLC expressed as a percen-
tage of the original length are given in Table 5.
It is worth noting that PLC or PVC is a cold to
cold-test measurement. The change in dimen-
sion may be substantially greater at high tem-
perature compared to the change detected by
measuring its size before and after firing.
Thermal conductivity (k) in W m71 K71 of
refractories may be determined using the static
guarded plate, dynamic hot wire, or dynamic
laser flash methods (Iseki, 1998). The ISO stan-
dard (ISO 8894 Part 2Ð90) describes the hot-
wire method. The thermal conductivity of
refractories is a complex function of chemical
composition and microstructure (e.g., porosity
and porosity distribution, grain morphology,
level, and type of aggregate±matrix bond) (see
Chapter 4.02, this volume). Typical values as a
function of temperature are given in Table 6.
Room temperature values can be as high as
40 Wm71 K71 for oxide±carbon containing
refractories measured parallel (//) to the gra-
phite flakes although only 20 W mK71 in the
same bricks measured perpendicular (\) to the
flakes. Clearly, the high-temperature values are
more important. In general, conductivity de-
creases at elevated temperatures because pho-
non transport is more difficult when atoms are
vibrating strongly. Additionally, in oxide±car-
bon refractories microstructural changes occur
in service by, e.g., reaction of metal additives so
that new phases such as forsterite or spinel
appear which reduce conductivity further. Re-
fractories with a high proportion of glassy
20 Refractories

Figure 14 Rising temperature RuL curves for refractory bricks: (a) fireclay, (b) sillimanite, (c) silica, and (d)
magnesia-chrome.

Figure 15 Creep RuL curves for refractory bricks, (a) sillimanite (65% alumina), (b) corundum (98%
alumina), (c) spinel-bonded magnesia-chrome, and (d) sintered (95%) magnesia.

phase and porosity (e.g., fireclay bricks,
Table 6) generally have a small positive gradi-
ent as the radiant heat transport mechanism
operating becomes slightly easier with increased
temperature.
4.12.4.3 Thermal Shock Resistance
Thermal shock can be defined as serious
cracking in components subject to rapid
changes in temperature (see Chapter 4.02, this
volume). Refractories often microcrack but if
this does not lead to mechanical failure of the
component it is not regarded as a problem.
Failure from thermal shock is caused by incom-
patible changes in dimension and failure occurs
in regions where the strain locally exceeds the
tensile failure strain. It generally occurs while
the material is brittle and is rare at temperatures
above 1100 8C where plastic flow can occur.
Thermal shock is aggravated by high thermal
expansion coefficients which induce larger
strains, nonlinear thermal expansion coeffi-
cients, e.g., arising from polymorphic changes
such as in quartz at 573 8C or noncubic phases,
low thermal conductivity, low strain to failure,
rapid heating or cooling, large component size,
uneven heating, and external mechanical load-
ing. Refractories with high thermal shock resis-
tance include carbon-bonded oxide graphite
systems and sialon-bonded SiC. Carbon-
bonded oxides have good thermal shock resis-
tance due to the high thermal conductivity of
carbon leading to reduced thermal gradients
and a microstructure which is resistant to
crack propagation. The absence of a brittle
ceramic bond and the requirement that cracks
meander around the graphite flakes markedly
reduces crack propagation.
 Thermomechanical Properties 21

Figure 16 Thermal expansion curves for a range of refractories.

Mathematical expressions for the thermally ulus, a = coefficient of thermal expansion, and
induced stress in materials of various shapes n = Poisson's ratio.
were summarized by Hasselman (1985). For DT is affected by the thermal conductivity (k)
shapes such as a constrained flat plate the of the material. This equation indicates that sth
peak stress typically occurring at the surface increases as E, a, and DT increase. For a given
on cooling is material E and a cannot be varied but we can
alter DT. From a materials point of view, DT
EaDT
sth ˆ …7† can be decreased by increasing the k of the
1ÿn material. The terms in this equation can be
where sth = thermal stress, E = Young's mod- rearranged to give a thermal shock resistance
parameter, R
s…1 ÿ n†
Table 5 PLC of representative refractories. Rˆ …8†
aE
Brick Time at temperature PLC (%) The R parameter estimates the DT (in 8C) that
the material can withstand prior to formation
Bauxite 2 h 1700 8C 71.3 of thermal shock cracks. Many other thermal
Carbon 2 h 1500 8C 71 shock resistance parameters have been derived
Magnesite 2 h 1800 8C 72 and summarized by Hasselman (1970) shown in
Chrome-magnesia 2 h 1800 8C 71
Table 7. The higher the value of the parameter
Corundum 2 h 1800 8C 71
Fireclay 2 h 1400 8C 70.5 the greater the resistance to crack initiation (for
Forsterite 2 h 1500 8C +0.5 R, R', and R@) or crack propagation (R@', R@@,
Mullite 2 h 1800 8C 70.3 and Rst). Parameters such as R consider the
Silica 2 h 1500 8C +0.5 difficulty of crack nucleation or initiation and
apply to fully dense ceramics and glass where

Table 6 Thermal conductivities as a function of temperature.

Brick Thermal conductivity (W m71 K71) at

25 8C 200 8C 600 8C 800 8C

Silicate bonded MgO 12 11 6.5 5

MgO±graphite (20%C) 21.1(\) 14.1(\) 13.8(\)
37.4(//) 30.9(//) 27.1(//)
Fireclay 1.6 1.7 1.9 2.0
Zircon 3.2 3.0 2.8 2.5
Silicate bonded high alumina 3 2.5 2.2 1.9
22
Table 7 Thermal shock resistance parameters.
Symbol Parameter
R s(17n)/aE
R' s(17n)k/aE
R@ s(17n)p/aE
R'@ E /s2(17n)
R@@ gE/s2(17n)
Rst (g/a2E )1/2
p = thermal diffusivity.
any thermal stress cracking must be avoided.
Parameters such as R@@ apply to situations
where cracks have already been nucleated.
This parameter considers the degree of crack
growth or propagation and is more relevant to
refractories that often contain a large flaw po-
pulation.
Thermal shock resistance is critical for many
refractory applications. Linings for high tem-
perature furnaces are exposed to large tempera-
ture gradients and must have good thermal
shock resistance. Refractory bricks contain
many pores and microcracks. Although, there-
fore, strength (s) is low cracks do not propagate
as predicted by parameters R@', R@@, and Rst.
However, in applications where thermal shock
cracks must be avoided altogether high strength
is required as predicted by R, R', and R@.
A typical thermal shock test for refractory
bricks involves firstly determining the Young's
modulus for the as-fired brick via a sonic test.
The brick is then subjected to an oxypropane
flame located a fixed distance from the brick
for a fixed time. The brick is then cooled to
room temperature and the sonic test repeated.
This is repeated until the sonic test shows clear
failure, i.e., when large cracks prevent signal
propagation.
Thermal shock resistance parameters can be
used for initial selection and screening of mate-
rials for a given thermal environment although
recently finite element (FE) methods have been
developed to determine thermal stresses which
combined with failure statistics can give a better
indication of the overall failure probability of a
component (Green, 1998). Bell (1992) describes
a series of tests for measuring physical proper-
ties of refractories enabling calculation of stres-
ses using FE methods for a complete furnace
lining including ceramic fiber gaskets, mortars,
vibratable mixes, and other components usually
neglected.
4.12.4.4 Refractories Failure Mechanisms
The properties described above, even those
measured at high temperature, may not be re-
Refractories
Units Parameter type
8C Initiation
Jcm71 s71 Initiation
cm2 8C s71 Initiation
Pa71 Propagation
cm Propagation
8C m71/2 Propagation
presentative of those of the refractory in service
due to changes bought about by reactions be-
tween the components of the refractory or with
the contents of the furnace. Refractory lining
lifetimes are usually limited by chemical corro-
sion, physical erosion, thermal shock failure
(Section 4.12.4.3), or a combination of these.
The main physical mechanisms of attack in-
clude abrasion on loading ore and scrap mate-
rials or erosion by particle-laden vapors moving
rapidly past the solid refractory. Abrasion is
particularly severe on loading iron blast fur-
naces with ore and steelmaking electric arc
furnaces with scrap metal. Erosion is a problem
in basic oxygen steelmaking furnaces when an
oxygen lance is used, in blast furnaces when the
tuyeres are in operation, and in glass tanks
(especially those that are gas fired). Regions
susceptible to this must therefore have high
hardness and toughness. Physical erosion can
also arise from the dynamic motion of the
furnace liquid contents. The microstructure of
the refractory may then be designed to contain
complex shaped phases which are not dislodged
easily by fluid flow such as ZrO2 dendrites in
the fused cast Al2O3±ZrO2±SiO2 linings of glass
tanks. A high level of physical or mechanical
interlocking of phases improves resistance to
physical wear.
Chemical attack involves reaction of the re-
fractory with penetrating fluids. This is usually
a dissolution reaction which can be either direct
in which atoms from the solid dissolve directly
and continuously into the liquid melt or indirect
when a solute-rich boundary layer builds up at
the refractory±melt interface (Lee and Zhang,
1999). This layer can be solid and passivate
further attack of the refractory. Lifetime exten-
sion of refractories subject to chemical attack
can be achieved using two approaches. First, by
limiting liquid penetration by using dense,
tightly-textured microstructures or phases
which are not wetted by the adjacent liquids.
High-density, fused Al2O3±ZrO2±SiO2 blocks
are used in the glass contact areas of tanks for
production of flat and container glass. Since
carbon is not wetted by silicate liquids carbon-
bonded refractories are used extensively in iron
 References
and steel making furnaces. For example, MgO±
C is used in Basic Oxygen Steelmaking (BOS)
vessels and Al2O3±C in the hollow ware for
continuous casting of steel. Second, by limiting
dissolution. This can be achieved either by
saturating the liquid with respect to susceptible
phases of the solid so that, e.g., an MgO-rich
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Spalling is the general term for the cracking
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caused by stress resulting from sudden tempera-
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from mechanical forces. This may arise from
constraint or pinching due to, e.g., inadequate
thermal expansion allowance.
ACKNOWLEDGMENTS
I would like to acknowledge helpful discussions
on this topic with Dr. S. Zhang, Dr. D. A. Bell,
Dr. M. O. Warman, Dr. R. Henderson, and
Professor P. J. Withers.
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Comprehensive Composite Materials
ISBN (set): 0-08 0429939
Volume 4; (ISBN: 0-080437222); pp. 363±385