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Dewatering Refractory Castables

Article  in  American Ceramic Society Bulletin · July 2004

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Dewatering D Dense refractory castables are important
engineering materials. The particle-packing
design of these castables invariably results

Refractory in bodies with low porosity and permeability

levels, and, consequently, they have dewa-
tering difficulties during the first heat-up.1–5
Green castables contain water physically

Castables retained in capillary pores and chemically

bonded as cement hydrates. Therefore,
their dewatering must be conducted over a
wide temperature range, usually
>550ºC.5,6 The use of suitable drying
Thermogravimetric tests were used to routines is crucial to prevent the body from
being mechanically damaged through
compare the performance of ultra-low- excessive pressurization caused by the
cement high-alumina castables under several steam generated during the heating stage.
heating routines and air humidity conditions In practice, these temperature require-
during dewatering for the purpose of ments cause dewatering to proceed in
three stages:7
decreasing the risk of explosive spalling. • Evaporation of free water;
• Ebullition of free water; and
• Dehydration of cement products.
The intensity and duration of each stage
depend on the heating schedule applied
and the product features (permeability,
thermal conductivity, cement content, sur-
face/volume ratio, thickness, etc.).7,8
Particularly in the case of high-alumina,
Murilo D.M. Innocentini, Fábio A. Cardoso,
ultra-low-cement compositions,7–9 the
Antonio E.M. Paiva and Victor C. Pandolfelli
dehydration stage contributes only slightly
Dept. of Materials Engineering, Federal University of
to dewatering. The controlled removal of
São Carlos, São Carlos, São Paulo, Brazil
free water is, therefore, the most important
factor to prevent explosive spalling of
green bodies during heat up (Fig. 1).
Drying by evaporation typically occurs
while the body temperature is maintained
at <100ºC and depends on the features of
the porous network (porosity, pore size and
permeability) and on the water properties
(viscosity, density and surface tension) as
well as on the external conditions (furnace
temperature, relative humidity of the air and
exposure to air flows).7,9–15 Although
evaporation does not usually cause steam
pressurization risks, it is a time-consuming
process, which renders it unfeasible to
remove all the free water retained in large
castable bodies on an industrial scale.
On the other hand, ebullition starts when
the normal water boiling point (100ºC at 1
atm) is reached inside the castable. In this
regime, as water begins to boil, vapor
Fig. 1. Dewatering stages observed for two green high-alumina castables with and bubbles promptly develop throughout the
without free water gradually heated to >100°C.7,8 Data refer to samples containing bulk of the liquid. The vapor pressure acts
2 wt% calcium aluminate cement and cured at 50°C. as the main driving force to expel water
toward the body surface, accelerating the
drying rate.7 However, pressure buildups
during rapid heating schedules or in

©The American Ceramic Society American Ceramic Society Bulletin www.ceramicbulletin.org July 2004 9101
Dewatering Refractor y Castables

structures having low permeability levels may sometimes cause

stress to develop and hydraulic bonds to break, which occa-
sionally causes explosive disintegration or spalling of the
product.1–3,7–9
Therefore, optimized drying routines should take full advan-
tage of both vaporization processes, i.e., the low pore pressure
level during evaporation and the fast dewatering rate during
ebullition. As more water evaporates, less of it remains to boil,
which hastens the evaporation process and helps to minimize
the risk of steam spalling during the subsequent stage.7
This paper focuses on a comparison of the performance of
various heating routines designed to optimize the removal of
free water through the evaporation process. The effects of the
heating procedure, furnace temperature and relative humidity
conditions within the drying chamber have been investigated
on high-alumina, ultra-low-cement bodies. Mass-loss data and
temperature profiles inside the bodies have been experimen-
tally obtained and used to evaluate the best operational
conditions to maximize the removal of free water at <100ºC
and, hence, to minimize the risk of explosive spalling above this
temperature. The most economical heating programs have
been determined based on the cumulative energy consumption
measured during the tests.

MATERIALS AND METHODS

The castable composition chosen for this study consisted of a
mixture of 98 wt% alumina, 2 wt% calcium aluminate cement
(CA-14, Almatis, U.S.) and 4.52 wt% water (dry basis).
Almatis (U.S.) supplied the matrix powders (calcined aluminas
A1000 SG and A3000 FL, 22 wt%, dp < 100 µm, where dp is
the particle diameter). The aggregate grains (white fused alu-
minas, grades 4/10, 8/20, 10/36, 20/40 and 200F, 76 wt%,
dp < 4.5 mm) were supplied by Elfusa (Brazil). The particle-
size distribution of this composition was adjusted to a theoreti-
cal curve based on the Andreasen packing model, with a coef-
ficient of distribution (q) of 0.21, to obtain a potentially self-
flow castable.16
Samples were cast in 4 cm diameter  4 cm thick cylinders,
cured in sealed molds at 50ºC (relative humidity (RH) of
~100%) for 48 h and heat-treated for 6 h at 800°C to decom-
pose all the hydrates and to eliminate the bound water. During
casting, a thin K-type thermocouple (0.2 mm diameter) was
inserted into one of the samples to ~2 mm below the upper
surface to monitor the actual heating profile of the sample. To
focus the analysis on the removal of unbound water, the
samples were saturated with distilled water under vacuum for
2 h prior to each test.
Dewatering tests were conducted in an electric furnace (1700
W, EDG–Brazil) controlled using a proportional integral deriva-
tive (PID) system, according to various heating schedules.
The test sample was suspended in the center of the furnace
chamber (10  15  25 cm) to enable heat to reach every
face of the body simultaneously. In the first set of experiments,
the temperature profile in the saturated specimen was moni-
tored during each heating program. New tests then were
conducted on the sample without the thermocouple to monitor

©The American Ceramic Society American Ceramic Society Bulletin www.ceramicbulletin.org July 2004 9102
Dewatering Refractor y Castables

the water loss profile under the same heating conditions. Data
on mass and temperature were computer-recorded at 5 s
intervals throughout the experiments.
The mass loss during drying was assessed using the W
parameter, defined as

W(%) = 100[(Mo – M)/(Mo – Md)] (1)

where M is the instantaneous mass recorded at time ti during

the heating stage, Mo the initial mass and Md the dry mass of
the tested sample (previously determined in a test at 150ºC to
ensure the total removal of free water from the body).
The W parameter measures the cumulative fraction of water
expelled during the heat up per total amount of water initially
present in the body. W can vary from 0% (totally moist body) to
100% (totally dry body). The experimental drying rate during the
test is obtained using a numerical derivation of the W–t curve.
The operating variables used here were the heating proce-
dure, furnace temperature and humidity conditions inside the
furnace. The energy consumption of the furnace also was
computer-recorded throughout the tests.

WATER REMOVAL PERIODS

The removal of water from a rigid porous body by evaporation
under isothermal ambient conditions is divided into three well-
established periods.10–13
• In the constant-rate period (CRP), water is transported pri-
marily by capillary forces to the body surface, where it evapo-
rates into the atmosphere. The evaporation rate remains con-
stant as long as the flux of water maintains the liquid/vapor
meniscus stationary at the drying surface.
• In the first-falling-rate period (FRP1), the radius of the menis-
cus begins to recede into the porous network, which begins to
empty by water flowing through small pores and liquid layers
over the surface of the pores and by vapor diffusion. However,
as the partial pressure of water vapor in the voids reaches sat-
uration pressure, the steam must be removed from the voids
before further evaporation can take place, which makes the
diffusion process rate limiting at this stage and gradually
decreases the drying rate.
• In the second-falling-rate period (FRP2), the liquid pathway to
the surface becomes discontinuous, and slow dewatering, driv-
en mostly by vapor diffusion, follows until equilibrium is reached.
The features of the drying periods can be affected by the
heating routine applied in the furnace, especially during the
CRP, in which evaporation takes place on the body surface
and is highly sensitive to changes in the surrounding atmos-
phere. Thus, when the sample is exposed to a hotter environ-
ment, a transient thermal gradient is established in the body up
to equilibrium. During this period, the water viscosity (µliq) in
the pores gradually decreases, which favors the capillary
transport of liquid to the surface and a concomitant increase of
saturation water-vapor pressure (Pv), which enhances the rate
of evaporation to the atmosphere. Therefore, the overall drying
performance is expected to depend on the temperature set in
the environment and on the time it takes for the body to reach
this temperature.

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Dewatering Refractor y Castables

PLATEAU AND RAMP SCHEDULES

This effect was investigated for refractory castables heat-
ed according to two dissimilar routines up to the same
temperature of 60°C (Fig. 2(a)). In the first routine, called
the plateau schedule, the furnace temperature was
increased in 20 min from ambient (~30ºC) to 60ºC and
held there until 90% of the initial free-water content was
removed from the saturated sample. In the second rou-
tine, called the ramp schedule, the furnace temperature
was gradually increased from ambient to 60ºC over the
same total drying time that elapsed in the plateau sched-
ule (td = 360 min). In both cases, a forced stream of dry
air was fed into the furnace during the test.
As expected, the thermal responses in the body were
different during each routine (Fig. 2(b)). The higher
temperature gradient established in the first 20 min of the
plateau schedule accelerated the transfer of heat from the
furnace to the body and enhanced the mass loss (Fig.
2(c)). Thus, although the same initial and final furnace
temperatures were used, the fast-heating procedure
caused the removal of 90% of the free water, whereas the
gradual temperature increase (ramp schedule) yielded only
an 84% mass loss during an equal drying time.
The gradual increase in the castable temperature also
resulted in changes in the drying periods (Fig. 2(d)). The
faster heat-up during the plateau schedule enhanced the
evaporation rate on the body surface, which caused the
beginning of the drying process to be marked by a sharply
increased rate period (IRP) rather than by the usual CRP.
The peak at td ≈ 50 min represented the transitory equilib-
rium between the continuous increase in the evaporation
rate because of the temperature increase and the progres-
sive retreat of the drying front into the pores (beginning of
the FRD).
On the other hand, the castable heated slowly according
Fig. 2. Thermogravimetric data obtained for a drying process
to the ramp schedule displayed a longer but less sharp conducted at 60ºC according to two heating routines: (a) heating
IRP, and the transition to the FRP occurred at td ≈ 170 schedule in the furnace; (b) resulting temperature profile at the
min. Therefore, the plateau schedule proved consistently sample surface; (c) cumulative water-loss profile; (d) drying rate
more efficient in dewatering than did the ramp schedule, profile; and (e) heating rate profile at the sample’s surface.Tests
were conducted with a dry-air stream inside the furnace.
and the best comparative performance occurred after 115
min (Wplateau = 65% versus Wramp = 28%), which coin-
cided with the time during which the drying rate of the
former routine overtook that of the latter (Fig. 2(d)).
Because the steam formed in the drying front latently
stored most of the incoming heat, the outer layers of the
body were more efficiently heated only when the liquid
menisci receded into the porous network, which
decreased the thermal gradient with the environment. This
explained why the end of the IRP in the plateau and ramp
schedules was followed by a transitory increase in the
heating rate measured at the body surface (Fig. 2(e)).
Therefore, the location of the drying front along the body
thickness could be monitored by changes in the mass-loss
profile and by sharp increases in the temperature meas-
ured through the body.
However, when no mass-loss data were available for
analysis (as is usually the case in industrial contexts), it

©The American Ceramic Society American Ceramic Society Bulletin www.ceramicbulletin.org July 2004 9104
Dewatering Refractor y Castables
Fig. 3. Thermogravimetric data obtained for a drying process con-
ducted at 100ºC according to two heating routines: (a) heating
schedule in the furnace; (b) resulting temperature profile at the
sample surface; (c) cumulative water-loss profile; (d) drying rate
profile; and (e) heating rate profile at the sample surface.Tests
were conducted with a dry-air stream inside the furnace.
©The American Ceramic Society American Ceramic Society Bulletin
was important to make sure that the source of the thermal
signal actually came from the displacement of the drying
front and from no step adjustment in the furnace program.
The heating rate in the body following the plateau schedule
clearly increased during the first 20 min of testing (Fig.
2(e)), although it coincided with the time required by the
furnace to reach the steady state at 60ºC. The actual
heating rate increase associated with the drying front took
place only 40 min later and, thus, was unrelated to the
furnace heat up.
Another method to accelerate the dewatering process
was to increase the maximum working temperature set in
the environment, which accentuated the liquid capillary
transport and the evaporation rate in the body.10 This
investigation was conducted using tests with plateau and
ramp programs up to a final furnace temperature of 100ºC,
maintaining a dry-air stream (Fig. 3(a)).
Despite trends similar to those obtained in the tests at
60°C, dewatering was much faster at 100°C (Figs.
3(b)–(e)). Again, the plateau schedule yielded better
performance because of the more efficient heat transfer to
the body (Fig. 3(b)). The time required by the castable
sample to reach a cumulative mass loss (W) of 90% in the
plateau schedule was decreased to 158 min (56% lower
than at 60°C). Comparatively, W for the ramp schedule
during the same drying time was only 78% (Fig. 3(c)).
Although the furnace temperature was set at 100°C, no
drying stage related to the ebullition of free water (as
exemplified in Fig. 1) was observed (see curves in Fig.
3(d)). This was explained by the fact that the actual maxi-
mum temperature that reached the sample surface after the
158 min of the plateau schedule was only 95°C.
Nevertheless, the drying periods related to water evapora-
tion clearly changed. The higher furnace temperature
intensified the drying rate during the IRP, which also
anticipated the transition to the FRP in comparison with the
curves at 60°C. The plateau schedule yielded a higher
drying rate during the first 58 min of testing, but then was
surpassed by the ramp schedule. However, during this time,
water removal was clearly favored under the former routine
(Wplateau = 61% versus Wramp = 21%).
The thermal signals that related to the displacement of
the drying front were more pronounced in the tests at
100°C in both routines, which confirmed that the end of
the IRP was marked by an accelerated heating rate on the
body surface (Fig. 3(e)).
It is well established in the literature10,13 that the evapora-
tion rate (Revap) depends on the temperature and the
humidity condition in the environment.
Revap = k(Pv – PA) (2)
where k is a mass transfer factor that depends on the tem-
perature, draft and geometry of the system, Pv the vapor
pressure in the drying front and PA the ambient vapor
pressure.
As previously discussed, an increase in body and furnace
temperature leads to increases in k and Pv, which
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Dewatering Refractor y Castables

enhances the evaporation rate. On the other hand, if the drying

process is conducted within a closed chamber, without an
efficient exhaust system, the released vapor accumulates in the
environment, which increases PA and decreases the driving
force for evaporation during the CRP or IRP. The RH in the
environment at a given temperature can be expressed by

RH(%) = 100(PA/Pv) (3)

where Pv depends only on the temperature of the system,

according the Antoine equation.7 Therefore, RH is a direct
measurement of the amount of water that can be effectively
introduced into the atmosphere at a given temperature.

INFLUENCE OF HUMIDITY
The influence of a higher RH on the drying performance was
investigated in a new series of plateau experiments at 60 and
100°C, albeit with a constant humid-air stream within the fur-
nace chamber.
In a humid environment, the drying rate was
decreased and the effect was more pronounced at
lower furnace temperatures (Fig. 4). Contrary to the dry-
air test at 60°C, which showed a direct transition from
IRP to FRP after 50 min, the humid-air test at 60ºC
showed that the IRP was initially followed by a relatively
large CRP, after which it entered the FRP at td = 85
min. Therefore, in this case, the driving force for
evaporation into the atmosphere was lower, and the
drying front remained at the body surface for a longer
time, but it was less effective in terms of mass loss. As
a comparison, after td ≈ 85 min, Wdry = 52% versus
Whumid = 41% in the experiment at 60ºC.
At 100°C, the effect of air humidity on the drying
stages was drastically decreased (Fig. 4). No CRP was
observed in either curve, and the transition from IRP to
FRP started at approximately the same time. The only
detectable difference was a slightly lower drying rate at
td ≈ 30 min in the body tested in the humid-air furnace.
This effect was expected, because the increase in
furnace temperature to 100°C (actually 95°C in the
vicinity of the sample) allowed for more steam to be
retained in the atmosphere because of the simultaneous Fig. 4. Influence of the humidity conditions in the furnace on
increase in Pv and in the mass transfer factor k. Had the normal the drying-rate profiles obtained for the plateau schedules at
boiling point of water actually been reached, the air humidity 60 and 100°C.
would no longer have been an important parameter, because
ebullition would have taken place in the drying front, regardless
of the external conditions, and the equilibrium moisture in the
body would have been low.
In this limit situation, which characterized the beginning of the
ebullition stage (Fig. 1), the pressure gradient of the generated
steam became the main driving force for dewatering, which
placed vapor diffusion and capillary flow factors in a secondary
position. Therefore, in practice, the hastening of the evaporation
process was favored by heating schedules that rapidly reached
100°C in the castables, because they enhanced the evapora-
tion rate and decreased the dependence on external humidity

©The American Ceramic Society American Ceramic Society Bulletin www.ceramicbulletin.org July 2004 9106
Dewatering Refractor y Castables
Fig. 5. Comparative performance of the four heating
programs tested in this work under a dry-air stream
within the furnace: (a) cumulative water-loss profile and
(b) cumulative energy consumption.
©The American Ceramic Society American Ceramic Society Bulletin
conditions. Furthermore, at this temperature, the steam
pressure in the pores was already sufficiently high to
accelerate dewatering but too low to damage the
porous structure.
ENERGY CONSIDERATIONS
A comparative analysis of the drying performance and
the energy consumed in the four heating routines was
evaluated (Fig. 5). Only the dry-air tests were consid-
ered. In general, dewatering was enhanced by rou-
tines that provided either a faster initial heat-up
(plateau schedules) or a higher temperature in the fur-
nace (100°C). For shorter testing times (td < 120
min), the plateau schedules at 60 and 100°C provid-
ed more efficient dewatering, although the ramp
schedule at 100°C also was effective with longer
times. The least effective case was the ramp sched-
ule at 60°C, which provided no favorable conditions for fast
evaporation in the body.
As expected, the routines at 100°C consumed more energy,
particularly the plateau schedule, in which the furnace tempera-
ture was maintained longer at this level. On the other hand, the
ramp schedule at 60°C was economical, although it did not
produce the desired effect on dewatering. The best compro-
mise between an effective and an economical routine, however,
depended on the particular requirements of each process in
terms of energy and time to dry the product. ■
Acknowledgments
The authors are grateful to the Brazilian research funding institution FAPESP and
to Alcoa–Brazil and Magnesita S.A. for supporting this work.
References
1R.E. Moore, J.D. Smith,W.L. Headrick Jr. and T.P. Sander,“Monolithic Dewatering
Theory Testing and Practice: New Challenges”; presented at the 32nd Annual
Symposium on Refractories, St. Louis Section of the American Ceramic Society, St.
Louis, Mo., Mar. 1996.
2P. Kalifa, F.D. Menneteau and D. Quenard,“Spalling and Pore Pressure in HPC at
High Temperatures,” Cem. Concr. Res., 30, 1915–27 (2000).
3W.E. Lee and R.E. Moore,“Evolution of in Situ Refractories in the 20th
Century,” J.Am. Ceram. Soc., 81 [6] 1385–410 (1998).
4M.Velez,A. Erkal and R.E. Moore,“Computer Simulation of the Dewatering of
Refractory Concrete Walls,” J.Tech.Assoc. Refract. Jpn., 20 [1] 5–9 (2000).
5M.D.M. Innocentini, C. Ribeiro, J.Yamamoto,A.E.M. Paiva, L.R.M. Bittencourt, R.P.
Rettore and V.C. Pandolfelli,“Drying Behavior of Refractory Castables,” Am. Ceram.
Soc. Bull., 80 [11] 47–56 (2001).
6M.D.M. Innocentini, C. Ribeiro, L.R.M. Bittencourt and V.C. Pandolfelli,“Fluid
Dynamics and Thermal Aspects of the Dewatering of High-Alumina Refractory
Castables: Removal of Physically Absorbed Water,” J.Am. Ceram. Soc., 84 [11]
2696–98 (2001).
7M.D.M. Innocentini, F.A. Cardoso, M.M.Akyioshi and V.C. Pandolfelli,“Drying
Stages during the Heat-Up of High-Alumina, Ultra-Low-Cement Refractory
Castables,” J.Am. Ceram. Soc., 86 [7] 1146–48 (2003).
8F.A. Cardoso, M.D.M. Innocentini, M.M.Akyioshi,V.C. Pandolfelli and L.R.M.
Bittencourt,“Scale-Up Effect on the Drying Behavior of High-Alumina Refractory
Castables,” J.Tech.Assoc. Refract. Jpn., in press.
9F.A. Cardoso, M.D.M. Innocentini, M.F.S. Miranda, F.A.O.Valenzuela and V.C.
Pandolfelli,“Drying Behavior of Hydratable Alumina-Bonded Refractory Castables,"
J. Eur. Ceram. Soc., 23 [4] 226–30 (2003).
www.ceramicbulletin.org July 2004 9107
 Dewatering Refractor y Castables

10G.W. Scherer,“Theory of Drying,” J.Am. Ceram. Soc., 73 [1] 3–14 (1990).

11S.Whitaker,“Simultaneous Heat, Mass and Momentum Transfer in Porous
Media:A Theory of Drying,” Adv. Heat Mass Transfer, 13, 110–203 (1977).
12D.A. Donatti,A.I. Ruiz and D.R.Vollet,“A Kinetic Study of Drying of TEOS-

Derived Gels Under Nearly Isothermal Conditions,” Mater. Res., 2 [1] 43–47
(1999).
13W.J. Coumans,“Models for Drying Kinetics Based on Drying Curves of Slabs,”

Chem. Eng. Process., 39, 53–68 (2000).

14R. Misra,A.J. Barker and J. East,“Controlled Drying to Enhance Properties of

Technical Ceramics,” Chem. Eng. J., 86, 111–16 (2002).

15W.C.J.Wei and C.L. Hsieh,“Drying Kinetics of Ultrafine Alumina Cake with

Drying Control Chemical (DCC),” J. Ceram. Soc. Jpn., 107 [4] 313–17 (1999).
16M.D.M. Innocentini,A.R. Studart, R.G. Pileggi and V.C. Pandolfelli,“How PSD

Affects the Permeability of Castables,” Am. Ceram. Soc. Bull., 80 [5] 31–36 (2001).

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