J. Am. Ceram. Soc.

, 85 [6] 151721 (2002)

journal

Permeability of High-Alumina Refractory Castables Based on

Various Hydraulic Binders
Murilo D. M. Innocentini, Arturo R. F. Pardo, and Victor C. Pandolfelli*
Department of Materials Engineering, Federal University of Sao Carlos, Sao Carlos, Sao Paulo 13565905, Brazil

Bruno A. Menegazzo
Alcoa Alumnio S.A., Sao Paulo, Sao Paulo 05804900, Brazil

Luis R. M. Bittencourt and Roberto P. Rettore

Magnesita Research Center, Contagem, Minas Gerais, 32210050, Brazil
This work investigated the changes in the permeability of
high-alumina self-flowing refractory castables based on calcium aluminate cement (CAC) and hydratable alumina binder
(HAB) pretreated between 110 and 1650C. Permeability
constants k1 and k2 were fitted from Forchheimers equation
based on airflow tests conducted at room temperature. The
results indicated that dehydration was the main contributing
factor for increased permeability in bodies pretreated up to
600C and that sintering effects prevailed between 900 and
1650C. Castables based on HAB were less permeable than
those based on CAC, a behavior ascribed to the type of
hydrates formed and to the particle-packing features of the
matrix and the matrixaggregate interfaces.
I.

sintering, providing information on the causes of the different fluid

dynamic performances mentioned in the literature for CAC- and
HAB-based castables.4
II.

Experimental Procedure

(1) Sample Preparation

For this investigation, two castable compositions were prepared
with a mixture of calcined aluminas as matrix powders (dp 100
m), white fused alumina as coarse aggregate grains (dp 5.6
mm), and two types of hydraulic binders. The batch named CAC
contained 2 wt% of calcium aluminate cement (CA-270, Alcoa
Chemicals, Little Rock, AK) and the batch named HAB contained
2 wt% of hydratable alumina binder (Alphabond 300, Alcoa
Chemicals). The particle-size distribution of both compositions
was adjusted to a theoretical curve based on Andreasens packing
model. A coefficient of distribution q of 0.21 was chosen to obtain
potentially self-flowing castables.
Castables were prepared by gradually adding water to the dry
raw materials in a planetary mixer for 10 min. An optimum
content of 0.26 mg/m2 of citric acid (Labsynth, Brazil) was added
to promote the dispersion of fine particles during mixing. Table I
summarizes the tested compositions.
Samples were cast as cylindrical disks (7.5 cm diameter 2.5
cm thickness) for permeability measurements and as bars (2.5
cm 2.5 cm 15.0 cm) for mechanical strength and porosity
tests. The samples were cured at 25C in a moistened environment
for 24 h, heat-treated in an electric furnace for 12 h at temperatures
of 1101650C (1C/min to 300C, 2C/min to 900C, and
3C/min to 1650C), and cooled to room temperature inside the
furnace.

Introduction

development of high-alumina castables based on ultra-lowcement, on calcia-free, and, more recently, on binder-free
compositions has resulted in remarkable gains in refractoriness and
mechanical properties at high temperatures, through the decrease
of the amount of low-melting-point phases in the aluminasilica
calcia ternary system.13 However, formulations of improved
particle-packing design, particularly those based on high-strength
binders, are almost invariably lower in porosity and permeability
than the products they replace. Numerous studies have suggested
that this is the reason these castables are relatively more difficult
to dewater, increasing the likelihood of explosive spalling during
the initial heat-up.4,5 In addition to this problem, the literature has
not yet established conclusively whether, in this case, the low
permeability level of green castables remains after their sintering
at high temperatures, ensuring they are less vulnerable to infiltration by corrosive fluids and, thus, a longer service life for
monolithic products in foundries and steelmaking plants.
In the present work, the permeability to airflow of high-alumina
self-flowing castable compositions based on a commercial calcium
aluminate cement (CAC) and a hydratable alumina binder (HAB)
was measured at room temperature in samples pretreated between
110 and 1650C. The objective was to assess the permeability
changes caused by thermal phenomena, such as dehydration and
HE

(2) Physical Characterization

Permeability to air flow was measured at room temperature
using an apparatus described elsewhere.6 Permeability constants
Table I.

Compositions of Tested Castables

Material

Calcined aluminas
White fused aluminas
Calcium aluminate cement
Hydratable alumina binder
Water (dry weight basis)

D. P. Buttcontributing editor

Manuscript No. 188030. Received January 8, 2001; approved March 11, 2002.
Supported by the Brazilian research funding institutions FAPESP and CNPq and
by Magnesita S.A. and Alcoa S.A., Brazil.
*Member, American Ceramic Society.

Castable composition (wt%)

CAC
HAB

22.79
75.11
2.00

22.57
75.43

4.93

2.00
4.12

A1000 SG, A3000 FL, APC3017 SG, Alcoa Alumnio S.A., Brazil. AEB 4/10,
8/20, 10/36, 20/40, 8/F, 40/F, 60/F, 200/F, Alcoa Alumnio S.A. CA 270, Alcoa
Chemicals, Little Rock, AK. Alphabond 300, Alcoa Chemicals.

1517

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Journal of the American Ceramic SocietyInnocentini et al.

Vol. 85, No. 6

were calculated from Forchheimers equation, expressed for flow

of compressible fluids as6 9
P i2 P2o

vs vs2
2Po L
k1
k2
where Pi and Po are, respectively, the absolute air pressures at the
entrance and exit of the sample, vs the fluid velocity, determined
by dividing the exiting volumetric flow rate by the total free-flow
area (25.4 cm2), L the sample thickness, the fluid viscosity, and
the fluid density, evaluated for Po 690 mmHg (0.092 MPa)
and T 25C. The parameters k1 and k2 are, respectively, the
Darcian and non-Darcian permeability constants.7,9
The first term of Forchheimers equation (vs/k1) represents
viscous energy losses and prevails at low fluid velocities, while the
second (quadratic) term (vs2/k2) represents kinetic energy losses
and is more significant at higher velocities. The relative contribution of each term on the total pressure drop also depends on the
values of k1 and k2, which can change significantly during the
thermal treatment because of phenomena that modify the porous
structure, including dehydration, thermal expansion mismatch,
sintering, and microcracking.
k1 and k2 were obtained by fitting the experimental data of
(P2i P2o)/2PoL vs vs in Eq. (1), using the least-squares method. At
least 15 sets of Pi, Po, and vs values were acquired in a stationary
airflow regime for each test, and three samples of each castable
were tested to ensure data reliability.
Apparent porosity was determined using the waterdisplacement method, based on the Archimedes principle (Standard Test Methods for Apparent Porosity, Water Absorption,
Apparent Specific Gravity, and Bulk Density of Burned Refractory
Brick and Shapes by Boiling Water, ASTM Specification C20
00. American Society for Testing and Materials, West Conshohocken, PA). Mercury porosimetry (Model No. 9320 PoreSizer,
Micromeritics Instrument Corp., Norcross, GA) provided data of
pore-size distribution of bodies treated between 1200 and
1650C. The microstructural observation was conducted using
scanning electron microscopy (SEM; Model No. 440 Stereoscan,
Leica Microsystems, Cambridge, U.K.) on gold-coated samples.
The mechanical strength (f; 25 mm 25 mm 150 mm
samples) was determined through modulus of rupture measurements (Standard Test Method for Cold Crushing Strength and
Modulus of Rupture of Refractories, ASTM Specification C133
94.), using a three-point bending device (span 140 mm,
displacement rate 10 mm/min, Model 810, MTS Systems,
Minneapolis, MN). The results were based on an average of five
samples for each temperature.
III.

Results and Discussion

(1) Dehydration Effects

Figure 1 illustrates the influence of the thermal treatment on k1
and k2. The permeability increase observed for CAC-bonded
castables up to 600C may be partially associated with the changes
in crystal structure and density of the hydrates present in the
calciaaluminawater system cured at 25C, especially of CAH10
(1720 kg/m3) and C2AH8 (1950 kg/m3), which rapidly convert to
C3AH6 (2520 kg/m3) above 110C.10-12 The latter hydrate, in turn,
reacts with AH3 (2420 kg/m3) to yield mostly C12A7 (2690 kg/m3)
at 600C.10 14 This sequence of reactions leads to an increase in
the porosity of the matrix paste, contributing to the increased
permeability shown in Fig. 1.15
Comparatively, the curing of HAB-based castables yields
large amounts of gel and crystalline AH3 (2420 kg/m3) as
hydrated phases. The agglutinative alumina gel contributes to

Cement notation: C is CaO; A is Al2O3; and H is H2O.

Fig. 1. Influence of thermal treatment on the permeability of highalumina refractory castables: (a) Darcian permeability constant k1 and (b)
non-Darcian permeability constant k2 (deviation bars refer to an average of
three samples for each temperature).

fill interstitial pores in the matrix paste.10,13,15,16 Thus, although thermal treatment leads to the formation of denser
alumina phases (3980 kg/m3), the greater consolidation of the
matrix ensures a lower permeability level throughout the
dehydration process.
In addition to the changes in the matrix properties, other
microstructural features relating to the castables particle packing exert a significant effect on permeability. Ideally, a castable
should be considered as a two-phase composite, comprised of a
matrix paste surrounding a skeleton of coarse aggregate grains.
However, because of the packing constraints imposed by the
aggregate surface, a region of higher porosity is formed at the
matrixaggregate interface.1719 The thickness and porosity of
this interfacial zone depends on the relative size of matrix
particles and aggregates and on the strength of the chemical
bonds provided by the cement hydrates. This type of arrangement of matrix around aggregates produces a gradient of
properties, particularly those involved in fluid flow.18,19 The
large pores at the interface offer much less resistance to the
diffusive and convective transport of fluids than do the matrix
pores.
The HAB and CAC compositions tested in this work are based
on the same size distribution of matrix and aggregates, resulting in
castables with similar amounts of interfacial pores. However, the
features of the hydraulic binder used may have influenced the
thickness of the porous zone at the interface. In the HAB-based
castables, the small particle size of the Alphabond 300 (d50 2.2
m and d90 5.0 m) and the formation of AH3 gel may have
ensured better packing in the interfacial region, a further reason for
the lower permeability level compared with the samples based on
CA-270 (d50 4.2 m and d90 35 m).
One important implication of this analysis regards the use of
permeability results obtained for prefired samples to distinguish
between the dewatering behaviors of green HAB and CAC
castables. In reality, there is a significant difference between
the air flowing through the castable structure during a permeability test and the water vapor being driven off it during an
actual dewatering process. In the former case, air percolates
through the shortest and fastest pathways, which are mainly
located in the interfacial zone,18 as previously discussed.
Therefore, permeability is expected to be very sensitive to
variations in the number of interfaces, which depend on the

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Permeability of High-Alumina Refractory Castables Based on Various Hydraulic Binders

1519

Fig. 2. Influence of thermal treatment on the apparent porosity of

castables (deviation bars refer to an average of three samples for each
temperature).

volumetric fraction and size distribution of aggregates in the

castable. On the other hand, during the dewatering process, the
steam must percolate a more difficult path, first exiting the
pores within the matrix bulk, where it is generated by the
boiling of free admixing water, and then percolating through the
interfacial zone to exit from the castable. In this case, the denser
the bulk of the matrix, the slower the release of steam.
An electrical analogy can be used here to distinguish between
the castables resistance to airflow and its resistance to steam
release. The forces of resistance to airflow are aligned in parallel
(either through the matrix or the matrixaggregate interfaces),
whereas the forces of resistance to steam release are aligned in
series (first the matrix, then the interfaces). Hence, the overall
resistance to dewatering is always higher than to airflow, which
explains why the permeability constants of prefired samples are
only partially successful in assessing the drying behavior of green
refractory castables. Hence, castables containing the same aggregate distribution can present a comparable airflow behavior, albeit
with different performances for dewatering, which are expected,
depending on the cement type, water content, and other matrix
modifiers.
(2) Sintering Effects
Although dehydration is the major contributing factor for
increased permeability in castables preheated to 900C, the
sintering effects above this temperature begin to control the
changes in the castables properties.
The effect of sintering on permeability is strongly dependent on
the changes in porosity and pore shape that occur in the castable
throughout the thermal treatment. Sintering causes densification
and, usually, some volumetric change in the matrix bulk. On the
other hand, the skeleton of fused aggregate grains is inherently
slightly reactive only in the compositions studied here and normally undergoes reversible thermal expansion effects during the
sintering process. However, during heating, the relative movement
caused by the simultaneous densification of the matrix and the
reversible expansion of aggregates may, after cooling, result in a
further detachment of the boundaries between matrix and aggregates, where the more permeable pores of the castable are located.
From a fluid dynamics standpoint, the overall result of such
phenomena is an increase in the flow resistance through the matrix,
which is already less permeable at lower temperatures, and a
decrease in the resistance through interfacial pores, which are the
main flow path in the castable. Therefore, unless strong and
thermally stable adhesion is provided between aggregates and
matrix, a fraction of interfacial permeable pores always remains
after cooling, and the expected net effect of sintering is a relatively
high permeability level of burned bodies.
This hypothesis is reinforced by the results illustrated in Fig.
1. Thermal treatment promoted a more pronounced increase in
permeability constants above 900C. HAB and CAC samples
displayed similar trends, although the use of hydratable alumina
as hydraulic binder resulted in significantly lower permeability

Fig. 3. Pore-size distribution obtained using mercury porosimetry for

castables treated above 1200C.

levels. Comparatively, for these two castables, the Darcian

constant k1 increased by 50% with treatments between 110 and
600C and by 50 times between 900 and 1650C. In these two
intervals, the non-Darcian constant k2 increased, respectively,
by 248% and by almost 4 orders of magnitude. Two important
conclusions could be inferred from these results. First, the
results confirmed that sintering did, in fact, exert a much
stronger effect than dehydration on the permeability of pretreated castables. Second, the results corroborated that the
greater increase in constant k2, especially above 900C, was
indirect evidence that the net permeable porosity became less
resistant to airflow because of a greater contribution of interfacial pores.7
No conclusive difference in apparent porosity was verified in
castables bonded with Alphabond 300 and CA-270, as shown in
Fig. 2. On the other hand, a mercury porosimetry analysis (Fig.
3) confirmed that pore size increased progressively in both
castables as the thermal treatment temperature increased from
1200 to 1650C. This suggested that sintering caused a
decrease in the fraction of small-sized voids within the matrix
bulk, which was, however, accompanied by the appearance of
larger and more-permeable pores, by the coalescence of matrix
pores, and/or by a further detachment at the matrixaggregate
interface.
The detachment possibility was confirmed by microstructural
SEM observations of samples treated at 1650C. The SEM results
in Fig. 4 show the existence of detachments in matrixaggregate
interfaces in both types of castables.
Figure 5 illustrates the influence of thermal treatment on
mechanical strength. In general, f decreased throughout the
dehydration process through the loss of chemical bonds between matrix particles in the castable. The relatively low f
level in CAC bodies at 300C occurred within the typical
temperature range for most of the dehydration reactions of
CACs.10 Accordingly, an evident decrease in f was observed
for HAB-based samples pretreated at 600C, which coincided
with the temperature suggested for the decomposition of AH
and AH3 hydrates. On the other hand, sintering conducted
above 900C promoted structural densification and consequent
gains in strength.
The above-described trends lead to the following remarks.
(1) The decrease of f in HAB and CAC castables took place
in a temperature range in which the bodies were only slightly
permeable, which represents two major favorable conditions for
the occurrence of spalling in green castables subject to the
dewatering process.
(2) Although the sintering process promoted densification,
which resultied in the improved strength of both castables, it also
produced bodies with high levels of permeability. Figure 6 shows
that, regardless of the cement type used, there was a clear

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Journal of the American Ceramic SocietyInnocentini et al.

Fig. 4.

Vol. 85, No. 6

SEM micrographs of refractory castables treated at 1650C: (a) CAC and (b) HAB.

correlation between the gains in mechanical strength and the

increase in k1 and k2 caused by thermal treatment.

IV.

Fig. 5. Flexural strength of prefired high-alumina refractory castables

(deviation bars refer to an average of five samples for each temperature).

Conclusions

The purpose of this work was to investigate the causes of

permeability changes resulting from the thermal treatment of
high-alumina castables based on various types of hydraulic binders. The results showed that dehydration was an important contributing factor for permeability increases in bodies pretreated up
to 600C. Castables based on HAB were less permeable than those
based on CAC, and this behavior was attributed to the particlepacking features of the matrix and the matrixaggregate interface.
In bodies treated from 900 to 1650C, sintering caused densification of the matrix bulk, which resulted in changes in the size of
permeable voids in the castable, particularly because of detachment in the interfacial zone between the matrix bulk and aggregates, which caused a remarkable increase in permeability. A
correlation was verified between the gains in mechanical strength
and the increase in k1 and k2.
References
1

Fig. 6. Relationship between permeability constants and flexural strength

of refractory castables prefired at various temperatures (lines refer to
exponential fittings).

W. E. Lee and R. E. Moore, Evolution of in Situ Refractories in the 20th

Century, J. Am. Ceram. Soc., 81 [6] 1385410 (1998).
2
A. R. Studart, W. Zhong, and V. C. Pandolfelli, Rheological Design of
Zero-Cement Self-Flow Castables, Am. Ceram. Soc. Bull., 78 [5] 6572 (1999).
3
W. Ma and P. W. Brown, Mechanisms of Reaction of Hydratable Aluminas,
J. Am. Ceram. Soc., 82 [2] 45356 (1999).
4
M. W. Vance and K. J. Moody, Use of Hydratable Alumina Binders in Refractory
Compositions and Related Applications; presented at the 97th Annual Meeting of the
American Ceramic Society, Cincinnati, OH, May 1, 1995.
5
R. E. Fisher, Permeability/Dehydration Behavior of Superduty Class Castables,
Am. Ceram. Soc. Bull., 59 [7] 702705 (1980).
6
A. R. F. Pardo, Permeability of High-Alumina Self-Flow Refractory Castables
(in Portuguese); M.Sc. Thesis. Department of Materials Engineering, Federal University of Sa o Carlos, Brazil, 2000.
7
M. D. M. Innocentini, A. R. Studart, R. G. Pileggi, and V. C. Pandolfelli, PSD
Effect on the Permeability of Refractory Castables, Am. Ceram. Soc. Bull, 80 [5]
3136 (2001).
8
M. D. M. Innocentini, A. R. F. Pardo, V. R. Salvini, and V. C. Pandolfelli, How
Accurate is Darcys Law for Refractories, Am. Ceram. Soc. Bull., 78 [11] 64 68
(1999).
9
M. D. M. Innocentini, A. R. F. Pardo, and V. C. Pandolfelli, Influence of Air
Compressibility on the Permeability Evaluation of Refractory Castables, J. Am.
Ceram. Soc., 83 [6] 1536 38 (2000).

June 2002
10

Permeability of High-Alumina Refractory Castables Based on Various Hydraulic Binders

K. M. Parker and J. H. Sharp, Refractory Calcium Aluminate Cements, Trans.

J. Br. Ceram. Soc., 81, 35 42 (1982).
11
F. M. Lea, The Chemistry of Cement and Concrete; pp. 177244. Edward Arnold,
London, U.K., 1983.
12
G. V. Givan, L. D. Hart, R. P. Heilich, and G. Maczura, Curing and Firing
High-Purity Calcium Aluminate-Bonded Tabular Alumina Castables, Am. Ceram.
Soc. Bull., 54 [8] 710 13 (1975).
13
P. Garce s et al., Effect of Curing Temperature in Some Hydration Characteristics of Calcium Aluminate Cement Compared to Those of Portland Cement, Cem.
Concr. Res., 27 [9] 134355 (1997).
14
N. Schmitt et a1., Coupling Between Kinetics of Dehydration, Physical, and
Mechanical Behaviour for High-Alumina Castable, Cem. Concr. Res., 30, 1597 607
(2000).

15

1521

S. A. Rodger and D. D. Double, The Chemical Hydration of High-Alumina

Cement in the Presence of Accelerating and Retarding Admixtures, Cem. Concr.
Res., 14, 73 82 (1984).
16
Y. Hongo, -Alumina-Bonded Castable Refractories, Taikabutsu Overseas, 9
[1] 3538 (1988).
17
D. P. Bentz, E. J. Garboczi, and P. E. Stutzman, Experimental and Simulation
Studies of the Interfacial Zone in Concrete, Cem. Concr. Res., 22, 891902 (1992).
18
D. P. Bentz, Fibers, Percolation, and Spalling of High-Performance Concrete,
ACI Mater. J., 97 [3] 35159 (2000).
19
K. L. Scrivener and K. M. Nemati, The Percolation of Pore Space in the Cement
Paste/Aggregate Interfacial Zone of Concrete, Cem. Concr. Res., 26 [1] 35 40
(1996).