G Model

JECS-10669; No. of Pages 11 ARTICLE IN PRESS

Journal of the European Ceramic Society xxx (2016) xxxxxx

Contents lists available at www.sciencedirect.com

Journal of the European Ceramic Society

journal homepage: www.elsevier.com/locate/jeurceramsoc

Mechanism of pore generation in calcium hexaluminate (CA6 )

ceramics formed in situ from calcined alumina and calcium carbonate
aggregates
Rafael Salomo a, , Veridiana Lopes Ferreira a , Ivone Regina de Oliveira b ,
Adriane D.V. Souza a , Wagner R. Correr c
a
Materials Engineering Department, So Carlos School of Engineering, University of So Paulo, Avenida Trabalhador So-carlense 400, So Carlos, SP, Brazil
b
Institute for Research and Development, University of Vale do Paraiba, Avenida Shishima Hifumi 2911, So Jos dos Campos, SP, Brazil
c
So Carlos Institute of Physics, Avenida Trabalhador So-carlense 400, So Carlos, SP, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Porous structures of calcium hexaluminate (CaAl12 O19 or CA6 ) are resistant to densication, chemical
Received 3 March 2016 attack and thermal shock and have been widely employed in thermal insulators for high temperatures
Received in revised form 11 May 2016 (above 1400 C). Despite its technological importance, little is known corcerning the in situ formation of
Accepted 15 May 2016
CA6 from the early calcination temperatures (500900 C) up to full sintering (above 1000 C). This study
Available online xxx
investigated the mechanisms of pores generation in in situ CA6 obtained from a mixture of calcined alu-
mina (-Al2 O3 ) and chemically precipitated calcium carbonate (CaCO3 ) aggregates. The evolution of the
Keywords:
microstructure was followed by scanning electron microscopy, X-ray diffraction, dilatometric analysis,
Calcium hexaluminate
Alumina
and measurements of physical properties, in the 5001500 C temperature range. Samples of 50-40% total
Calcium carbonate porosity and different degrees of linear expansion were obtained after sintering at 11001500 C, respec-
Porous structures tively. The crystallization of liquid phases of eutectic composition played a major role in the formation
and maintenance of pores after CaCO3 decomposition.
2016 Elsevier Ltd. All rights reserved.

1. Introduction Ca(OH)2 CaO + H2 O(Gas) (2)

420580 C

1.1. General aspects of the CaO-Al2 O3 system

The CaO-Al2 O3 system (or C-A) is an important input for the
production of two refractory materials, namely calcium aluminate
cements (CACs) and calcium hexaluminate (CaAl12 O19 , CaO6Al2 O3
or CA6 ) [14]. CACs are produced by solid-state reactions between
CaO and Al2 O3 sources (typical examples are calcium carbonate
and lime and bauxite or calcined alumina, respectively) that create
a mixture of different calcium aluminates (mainly C3 A, C12 A7 and
CA) [57]. Initially, the several possible precursor raw materials
decompose during the rst stages of heating (from 250 C up to
750 C), which results in a combination of Al2 O3 and CaO, according
to the general expressions
2Al(OH)3 Al2 O3 + 3H2 O(Gas)
250350 C
Corresponding author.
E-mail addresses: rsalomao@sc.usp.br, rslm@gmail.com (R. Salomo),
ivonero@univap.br (I.R. de Oliveira), wcorrer@gmail.com (W.R. Correr).
CaCO3 CaO + CO2(Gas) (3)
590753 C
As the heating proceeds, the compounds formed at around
1362 C are usually a mixture of C3 A, C12 A7 , and CA, which are the
phases of lowest melting point in the system (Fig. 1). The control of
the CaO-Al2 O3 ratio in the initial composition of the mixture and
the heating-cooling rates enables other phases, as CA2 , to be formed
along the reaction time [3,4,6,7]. After milling for granulometric
adjustments, such calcium aluminates behave as hydraulic binders
in castables and mortars for many refractory systems and varia-
tions in their proportion enable the design of cements of different
setting times [4,7].
(1) Differently from other calcium aluminates, CA6 does not react
with water and, therefore, is not suitable for cement production. On
the other hand, over the two past decades, it has became one of the
most important raw materials for refractories because of its unique
combination of resistance to slag corrosion, thermal shock, and
creep [812]. The next sections briey address such developments.

http://dx.doi.org/10.1016/j.jeurceramsoc.2016.05.026
0955-2219/ 2016 Elsevier Ltd. All rights reserved.

Please cite this article in press as: R. Salomo, et al., Mechanism of pore generation in calcium hexaluminate (CA6 ) ceramics formed in situ
from calcined alumina and calcium carbonate aggregates, J Eur Ceram Soc (2016), http://dx.doi.org/10.1016/j.jeurceramsoc.2016.05.026
G Model
JECS-10669; No. of Pages 11 ARTICLE IN PRESS
2 R. Salomo et al. / Journal of the European Ceramic Society xxx (2016) xxxxxx
Fig. 1. Phase diagram of the CaO-Al2 O3 system (adapted from [1,6]). Circles on the right side indicate the compositions and thermal treatment temperatures tested.
1.2. Routes for the obtaining of calcium hexaluminate
CA6 is obtained by high-temperature reactions (above 1300 C)
amongst sources of Al2 O3 (for instance, calcined [1,6,1317] and
tabular alumina [812], hydratable alumina (-Al2 O3 , [16,17]),
boehmite (AlOOH, [18]), Al(NO3 )3 [1922] and Al2 (SO4 )3 [23])
and CaO (CaCO3 [1,1317], Ca(OH)2 [16], CaO from dead-burnt
CaCO3 [6,16,24] and calcium aluminate cement [2529]) and dif-
ferent processing routes (solid-state reaction amongst compacted
raw materials [3,817], liquid-phase assisted sintering [1,20], sol-
gel synthesis [18], and soluble salt co-precipitation [1923]). For
a general view of this solid-state reaction, let us assume a per-
fectly dispersed agglomerate-free and random mixture of thin CaO
and Al2 O3 particles (or their precursors) combined to produce a
CaO:Al2 O3 molar ratio of 1:6. In this conguration, CaO particles
are most likely surrounded by Al2 O3 ones. The reaction begins at
around 10001100 C with the interdifusion of Ca2+ , Al3+ and O2
ions preferentially at the contact points amongst particles. Ca2+ ions
are diffused more rapidly into Al2 O3 than Al3+ in CaO, so that the
electrical neutrality of the system is kept [1,2,6,14,24,3033]. At
these contact spots and after a certain reaction time, the CaO-Al2 O3
ratio can be signicantly different from the total composition of
the system, therefore, low melting temperature compounds (C3 A,
C12 A7 and CA) begin to form around 1360 C, according to the
expressions:
CaO + 6Al2 O3 (1/3)Ca3 Al2 O6 + (17/3)Al2 O3
(1/3)Ca3 Al2 O6 + (17/3)Al2 O3 (1/12)Ca12 Al14 O33 +
(130/12)Al2 O3
(1/12)Ca12 Al14 O33 + (130/12)Al2 O3 CaAl2 O4 + 5Al2 O3
Above 1360 C, as the molten calcium-rich aluminates dissolve
the nearest Al2 O3 particles, the Al3+ concentration in the liquid
increases and forms CA2 :
CaAl2 O4 + 5Al2 O3 CaAl4 O7 + 4Al2 O3
As CA2 has a higher melting point than C12 A7 and CA, at
14001500 C temperature ranges, the liquid phase begins to crys-
Please cite this article in press as: R. Salomo, et al., Mechanism of pore generation in calcium hexaluminate (CA6 ) ceramics formed in situ
from calcined alumina and calcium carbonate aggregates, J Eur Ceram Soc (2016), http://dx.doi.org/10.1016/j.jeurceramsoc.2016.05.026
tallize in platelet grains [6,14,31,32]. After this point, no signicant
liquid phase is present in the system and the reaction continues as
a slower solid-state diffusion process up to the total consumption
of Al2 O3 and formation of CA6 :
CaAl4 O7 + 4Al2 O3 CaAl12 O19 (8)
The solid-state reactions that form CA6 and CA6 -Al2 O3 com-
posites depend fundamentally on the contact points amongst the
reactant particles. Therefore, they are affected mainly by four
parameters, namely type of CaO and Al2 O3 sources, degree of
proximity of the particles, average size ratio, and presence of impu-
rities or other compounds (particularly, MgO, SiO2 and Fe2 O3 )
[14,3436].
Reactions between non-oxide precursors, such as CaCO3 ,
Ca(OH)2 and Al(OH)3 usually produce highly asymmetric platelet
CA6 grains after an intense crystal growth along the basal plane
of the structure. Such a morphology preserves a signicant level
of inter-grain porosity. On the other hand, the combination of
stabilized oxide precursors (particles of dead-burnt CaO and of -
Al2 O3 ) generates a homogenous microstructure of equiaxial grains
and high levels of relative density [13,14,31,34]. Despite the lack
of deeper investigations on the early stages of those reactions
(between 1100 and 1500 C), previous studies suggested such dif-
ferences in the resulting microstructure can be attributed to the
average distance amongst the reactant particles. When particles
(4)
of carbonates and hydroxides are thermally decomposed, they
undergo a volumetric shrinkage and density increase due to the
release of CO2 and water, respectively [3742]. Therefore, part of
the space originally occupied by those particles in the compact
(5) becomes empty, which generates signicant levels of inter-particle
porosity. In a combination of CaCO3 and -Al2 O3 , for instance,
the CaCO3 decomposition increases the average inter-particle dis-
(6) tance and reduces the number of effective contact points amongst
the reactants. Because solid-state diffusion must occur through a
reduced number of contact points, such regions tend to form asym-
metrical CA6 crystals. Conversely, the mixing of CaO and -Al2 O3
produces no volumetric shrinkage and a large number of effec-
tive contact points behave as diffusion paths that generate more
(7)
equiaxial grains.
Imperfect contact points amongst Al2 O3 and CaO particles also
appear when the precursors have largely different average parti-
G Model
JECS-10669; No. of Pages 11 ARTICLE IN PRESS
R. Salomo et al. / Journal of the European Ceramic Society xxx (2016) xxxxxx 3

cle sizes and are poorly packed [14,16,34,35]. Therefore, whereas

isostatic hot-pressed parts of ne grained precursors, such as par-
ticles synthesized by sol-gel method or high energy-milled tend to
form more equiaxial grains, the sintering of coarse particles (nat-
ural CaCO3 or commercial lime, for instance) poorly packed by
uniaxial pressing or slip casting produces platelet crystals usually
followed by an extensive grain growth. Conversely, recent stud-
ies reported the use of particles of highly defect-rich surface (such
as -Al2 O3 ) can also produce structures of curved boundaries of a
smaller degree of asymmetry [16,17].
Lastly, impurities and other oxides also play a major role in the
development of the in situ CA6 microstructure. The roles of the
most common oxides found in refractory elds in CA6 formation
were studied recently. In CAC-bonded Al2 O3 -MgO-SiO2 castables
[2729,43,44], the processes of CA6 and spinel (MgAl2 O4 ) forma-
tion strongly affect each other, due to the competition for both Al3+
ions and room for accommodating their expansive products. The
presence of SiO2 (13 wt%) enabled the formation of a small con-
tent of liquid phase that favored the accommodation of CA6 crystals
and improved the densication of the system. Other mineraliz-
ing agents (Mg3 (BO3 )2 and TiO2 ) also produced more asymmetric
CA6 crystals, which favored the precipitation of aluminates at the
basal plane and modied the interactions of such crystals with the
surrounding particles and their densication.
The control of such parameters enables the design of microstruc-
tures with more or less asymmetrical grains and different levels of
residual porosity. Therefore, CA6 can be produced as lightweight
porous aggregates or monolithic parts (dense or porous) [812].

1.3. Calcium hexaluminate ceramics

The microstructure of dense ceramic parts produced by pre-

formed CA6 is comprised by equiaxial grains. Their outstanding
slag-corrosion resistance is the main technological advantage
[4,812]. However, in comparison to the in situ formed systems,
these materials require high compacting pressures and sinter-
ing temperatures are required, so that relative density levels
above 95% [14,34,45] can be achieved. Therefore, in the eld
of thermo-mechanical ceramics, a large number of studies has
focused on CA6 in situ formation as a toughening mechanism for
dense Al2 O3 composites and structural Al2 O3 -based refractories
[2530,34,43,4548]. This mechanism is based on two simul-
taneous effects [14,25,26,44,45]. Firstly, because of the density
mismatch (CA6 : = 3.7 g cm3 and Al2 O3 : = 4 g cm3 ), the CA6 for-
mation is an expansive process that generates a compression eld
throughout the sintered alumina matrix [37,41,42] and higher lev-
els of efforts are required for the nucleation of cracks originated
from tensile or exion forces. Secondly, the elongated CA6 grains
behave as crack deectors and bridging sites, which increase the
composites toughness and thermal shock resistance.
For a successful toughening of dense systems, the total ratio
of CA6 formed must range between 1 and 3 vol%, otherwise, the
excessive volumetric expansion and the large number of pores
formed deteriorate the properties of sintered alumina [43,44]. Con-
versely, porous ceramics can be produced entirely from in situ or
pre-formed CA6 . For thermal insulators, the densication resistance
and maintenance of high levels of porosity are more important than
mechanical strength and thermal shock resistance. In these applica-
tions, the heterogeneity of the grains and the volumetric expansion
of the in situ reaction can hinder the pores densication even when
exposed to high temperatures for long periods. Fig. 2. Raw materials employed: a) calcined alumina (-Al2 O3 ) and calcium carbon-
CA6 porous structures can be formed by the mixing of pre- ate (CaCO3 ) b) aggregates and c) primary particles.
formed materials and porogenic agents [15,49] or, more commonly,
by the microstructure changes that generate pores in the reactant
raw materials [10,14,16,17]. This is the case of structures produced
from the sintering reaction of compacted Al2 O3 (-Al2 O3 : calcined

Please cite this article in press as: R. Salomo, et al., Mechanism of pore generation in calcium hexaluminate (CA6 ) ceramics formed in situ
from calcined alumina and calcium carbonate aggregates, J Eur Ceram Soc (2016), http://dx.doi.org/10.1016/j.jeurceramsoc.2016.05.026
G Model
JECS-10669; No. of Pages 11 ARTICLE IN PRESS
4 R. Salomo et al. / Journal of the European Ceramic Society xxx (2016) xxxxxx

Fig. 3. Agglomerates of calcined alumina and CaCO3 (composition C1.0 A6 ) before pressing: topographic view (a-b) and EDS mapping (c) original image, d) cyan = Al; e) red = Ca;
f) overlay Al and Ca).

and tabular alumina; -Al2 O3 : hydratable alumina) and calcium
carbonate (CaCO3 ) or hydroxide (Ca(OH)2 ) particles. As discussed in
the previous section, the pores generated after the decomposition
of those hydroxides and carbonates are preserved during the sinter-
ing. Besides densication and chemical resistance, such structures
present a useful combination of a small average pore size (typi-
cally below 5 m [50,51]) and low thermal conductivity (around
0.4-0.6 W. (m.K)1 ) up to 1500 C. Therefore, they can be used as
thermal insulators, catalyst carriers, hot air and molten metal l-
ters and vessels for the storage of radioactive waste, amongst other
applications.
Despite the extensive discussion on the properties of sin-
tered CA6 porous ceramics (15001800 C), the evolution of their
microstructure at the early stages of the reaction sintering (from
room temperature up to 1500 C) has not been sufciently under-
stood. For instance, to the best of our knowledge, the role of the
liquid phases formation at 1365 C (molten C3 A, C12 A7 and CA) or
their further crystallization in CA2 and CA6 grains have never been
documented by scanning electron microscopy. Such knowledge
could improve the quality of the porous and dense CA6 -based struc-
tures and the renement of the processing parameters involved.
Therefore, the present study followed the microstructure evo-
lution and the reactions involved in the in situ formation of a
porous CA6 structure from calcined alumina and chemically precip-
itated calcium carbonate. From the early stages of heating (before
CaCO3 decomposition) up to the full sintering of the samples (at
1500 C), the phases formed, their morphology and the physi-
cal properties of the structures were accessed by means of X-ray
diffraction, dilatometric and thermogravimetric analyses, scanning
electron microscopy observations, and porosity and elastic mod-
ulus measurements. The results were analyzed according to the
phase diagram of the CaO-Al2 O3 system.
2. Experimental
2.1. Particles characterization
Particles were characterized through measurements of solid
density (Helium pycnometer method, Ultrapyc 1200e, Quan-
tachrome Instruments, USA), specic surface area (99.999 N2

Please cite this article in press as: R. Salomo, et al., Mechanism of pore generation in calcium hexaluminate (CA6 ) ceramics formed in situ
from calcined alumina and calcium carbonate aggregates, J Eur Ceram Soc (2016), http://dx.doi.org/10.1016/j.jeurceramsoc.2016.05.026
G Model
JECS-10669; No. of Pages 11 ARTICLE IN PRESS
R. Salomo et al. / Journal of the European Ceramic Society xxx (2016) xxxxxx 5

Fig. 4. Schematic representation of the pore-forming mechanism of the CaCO3 -Al2 O3 system.

adsorption, BET method, Nova 1200e, Quantachrome Instruments,
USA, ASTM C 1069-09 standard Standard Test Method for Specic
Surface Area of Alumina or Quartz by Nitrogen Adsorption.) and
average size (T-1202, Dispersion Technology Inc., USA; and eld
emission scanning electron microscopy, FEG-SEM, Inspect-F50,
FEI, Netherlands). Their chemical and phase compositions were
determined by X-ray dispersive spectroscopy (EDX 720, Shimadzu,
Japan) and X-ray diffraction (Rotaex RV 200B, Rigaku-Denki Corp.,
Japan; with K = Cu radiation, in the 10 to 90 2 range at a
2 min1 scan rate). The thermal decomposition of calcium car-
bonate was accessed by thermogravimetric analysis (TGA-Q50, TA

Please cite this article in press as: R. Salomo, et al., Mechanism of pore generation in calcium hexaluminate (CA6 ) ceramics formed in situ
from calcined alumina and calcium carbonate aggregates, J Eur Ceram Soc (2016), http://dx.doi.org/10.1016/j.jeurceramsoc.2016.05.026
G Model
JECS-10669; No. of Pages 11 ARTICLE IN PRESS
6 R. Salomo et al. / Journal of the European Ceramic Society xxx (2016) xxxxxx

Fig. 5. a) Total porosity, exural strength, b) linear variation, and c) linear variation rate for C0.0 A6 and C1.0 A6 samples thermally treated up to 1500 C; thermogravimetry
(b) mass loss and c) mass loss rate) for as-received CaCO3 particles.

Instruments, USA, 251000 C, 5 C.min1 heating rate and syn-
thetic air atmosphere).
2.2. Samples preparation
A mixture of calcined alumina and chemically precipitated
calcium carbonate clusters (Table 1, Fig. 2) was dispersed in iso-
propylic alcohol for the formation of a suspension containing 25
vol% of solids. 1 wt% dry-basis of organic binder (Butivar, Sigma,
Switzerland) was added to the suspension (a CaCO3 -free refer-
ence sample was also prepared under the same conditions). The
composition was ball-milled (10:1 ratio of 6 mm diameter zirconia
spheres, high-density polyethylene ask) for 1 h, so that the parti-
cles individualization could be improved (previous tests indicated
these conditions neither reduced the aluminas particles average
size signicantly nor broke calcium carbonate aggregates) and kept
overnight at 70 C for the evaporation of the isopropylic alcohol.
The dried powders were then sieved (DPart < 100 m) and uniaxially
pressed (40 MPa, 60 s) as 70 mm 20 mm 6 mm bars (for poros-
ity and elastic modulus measurements) and 8 mm length 6 mm
diameter cylinders (for dilatometric analyses). Such conditions
were previously determined to produce green samples of similar
total porosity level (50.5 0.5%).
All samples were measured and weighed before (initial length,
L0 ; initial width, W0 ; initial thickness, T0 ; initial mass, M0 ) and after
(nal length, LF ; nal width, WF ; nal thickness, TF ; nal mass, MF )
the thermal treatment (at 5001500 C, for 3 h, 1 C.min1 heating
rate, 10 C.min1 cooling rate). Their solid densities (S ) were mea-
sured in crushed equivalent samples (DPart < 100 m) by Helium
pycnometer method and their geometric total porosity (TP, %) was
calculated by Eq. (9) [4042]:
 
TP (%) = 100% 1 (Mi /Li Wi Ti Si ) (9)
The Youngs modulus (E, GPa) of red samples was measured
by the impulse excitation of vibration technique (Sonelastic, ATCP,
Brazil), according to the ASTM E 1876-01 standard (Standard Test

Please cite this article in press as: R. Salomo, et al., Mechanism of pore generation in calcium hexaluminate (CA6 ) ceramics formed in situ
from calcined alumina and calcium carbonate aggregates, J Eur Ceram Soc (2016), http://dx.doi.org/10.1016/j.jeurceramsoc.2016.05.026
G Model
JECS-10669; No. of Pages 11 ARTICLE IN PRESS
R. Salomo et al. / Journal of the European Ceramic Society xxx (2016) xxxxxx 7

Fig. 6. X-ray diffraction patterns for samples treated at different temperatures (a) 500 C, b) 700, c) 900 C, d) 1100 C, e) 1300 C, f) 1400 C1500 C). List of symbols
(JCPDS les):  = -Al2 O3 (461212); = CaCO3 (rhombohedral calcite, 862339);  = CaO (78-0673);  = CaAl4 O7 (Grossite or CA2 , 231037); * = CaAl12 O19 (Hibonite or CA6 ,
38-0470).

Table 1
Characteristics of the raw materials employed, compositions tested and theoretical phase evolution based on the CaO-Al2 O3 phase diagram.

Raw materials
a b
Physic-chemical properties Calcined alumina Calcium carbonate aggregates

Composition (wt.%) -Al2 O3 : 99.8; Na2 O: 0.05; Fe2 O3 : CaCO3 (calcite): 99.99;
0.01; MgO: 0.07; MgO: 0.01
SiO2 : 0.04; CaO: 0.03
Particle size (D50 /D90 , m) 0.5/2.3 Clusters: 3/7
Primary particles:
Thickness: 0.1 Length: 0.5
Solid density (, g cm3 ) 3.99 2.78
Specic surface area (m2 g1 ) 8.2 25.7
Humidity (wt.%, 150 C) 0.5 0.2
Loss of ignition (wt.%, 1000 C) <0.1 43.8

Compositions tested

Identication Alumina molar fraction (Al2 O3 /[Al2 O3 + CaO]) Composition before ring Theoretical composition of the
phases formed (at 1500 C)

Al2 O3 (%, wt./vol.) CaCO3 (%, wt./vol.) -Al2 O3 (wt.%) CaAl12 O19 (wt.%)

C0.0 A6 1.00 100/100 0.00/0.00 100 0.00

*
C1.0 A6 0.86 85.94/80.98 14.06/19.02 0.00 100
a
A1000 SG, Almatis, USA.
b
Synth, Brazil.
*
Theoretical composition to for calcium hexaluminate (CaAl12 O19 ).

Method for Dynamic Youngs Modulus, Shear Modulus, and Pois- Germany) equipment at a 5 C.min1 heating rate, up to 1500 C.
sons Ration by Impulse Excitation of Vibration). The phases formed at each thermal treatment temperature were
Dilatometric analyses were conducted in dried green samples identied by X-ray diffraction (crushed samples, DPart < 100 m)
(8 mm length 6 mm diameter cylinders) in DIL402C (Netzsch, and scanning electron microscopy (fractured surfaces) equipped

Please cite this article in press as: R. Salomo, et al., Mechanism of pore generation in calcium hexaluminate (CA6 ) ceramics formed in situ
from calcined alumina and calcium carbonate aggregates, J Eur Ceram Soc (2016), http://dx.doi.org/10.1016/j.jeurceramsoc.2016.05.026
G Model
JECS-10669; No. of Pages 11 ARTICLE IN PRESS
8 R. Salomo et al. / Journal of the European Ceramic Society xxx (2016) xxxxxx

with energy dispersive spectrometer (Apollo, EDAX, USA) for EDS novel pore-generation mechanism based on two types of interac-
mapping. tions amongst the elements of the microstructure [36].
Firstly, at 11001300 C, at the same time the Al2 O3 particles
began to sinter and increase the structures density, the spaces
3. Results and discussion
originally occupied by CaCO3 -CaO particles became partially empty
(Figs. 4 c and 7 ad). The SEM/EDS images (Fig. 8a and b) revealed
3.1. Raw materials characterization, green samples, and effects of
the pores showed a large concentration of calcium-containing com-
early thermal treatments (500900 C)
pounds at their borders (calcium aluminate CA2 was identied by
XRD, Fig. 6d and e). The localized formation of such compounds at
The as-received calcined alumina sample was comprised by cor-
the inner part of the pores occurred because of the high concen-
nered and irregularly shaped particles of -Al2 O3 (D50 = 0.5 m)
tration of Ca2+ ions at the Al2 O3 -CaO border. Due to the proximity
(Fig. 2a), whereas CaCO3 was formed by aggregates (D50 = 3 m,
of the particles, the solid-state interdifusion between Al2 O3 and
Fig. 2b) of ne rod-like precipitated rhomboedral calcite particles
CaO favored the generation of those low melting point aluminates.
(thickness of 0.1 m and length of 0.5 m, Fig. 2c). Such aggre-
The small portion of liquid phase formed was absorbed by the sur-
gates are typically found in products of soluble salt precipitation
rounding matrix and released the inner portion of the pore (Fig. 4d).
processes [50,52]. After the preparation of the compositions (dis-
Although the liquid-phase formation was theoretically predicted
persion in alcohol, drying, deagglomeration and sieving), the SEM
to occur above 1362 C, the presence of impurities (such as SiO2
observations of the resulting non-compacted powders showed they
and Na2 O) may have contributed towards reducing the minimum
were formed by 2030 m diameter agglomerates (Fig. 3a and
temperature for such reactions.
b). The EDS mapping of one of the agglomerates (Fig. 3cf) indi-
Secondly, the formation of calcium aluminates also caused a
cates most of the CaCO3 aggregates remained intact after mixing
signicant linear expansion at this temperature range. These com-
and became dispersed in a continuous calcined alumina matrix. A
pounds have lower density (CA = 3.2 g cm3 and CA2 = 3.4 g cm3 ,
schematic representation of this structure is shown in Fig. 4a.
respectively) in comparison to -Al2 O3 (4.0 g cm3 ) and CaO
Green samples showed a similar total porosity level (50.5 0.5%,
(3.5 g cm3 ), and, therefore, their formation is expansive. Other
Fig. 5a) because they were prepared under a same pressing con-
reports have described how these expansive reactions produce
dition and contained an identical amount of organic binder. This
cracks in dense structures, such as high-alumina castables bonded
result indicates any variation in the physical properties during a
with calcium aluminate cements [27,29,48]. In the present study,
thermal treatment can be attributed to the reactions that took place
on the other hand, this expansion minimized the densication of
amongst the particles.
the structure and produced no further mechanical damage.
Corundum (-Al2 O3 ) and calcite (CaCO3 ) were the only crys-
Between 1300 C and 1400 C, the liquid phase formed begins to
talline phases (Fig. 6a) for the CaCO3 -containing sample calcined at
dissolve more particles of the matrix (Figs. 4ef, 7eh, and 8c and d).
500 C, which indicates neither CaCO3 decarbonation, nor calcium
Therefore, the Al2 O3 ratio in the composition increased in the areas
aluminate formation occurred up to this point. At 700900 C, on
that surrounded the pores up to the total conversion of the sys-
the other hand, calcite peaks were signicantly reduced and the
tem into CA6 at 1400 C and 1500 C (Fig. 6f). Because the reactions
rst signs of lime (CaO) were indentied (Fig. 6b and c). Such results
occurred from the surface of the pores (of high CaO concentration)
are consistent with the thermogravimetric analysis (Fig. 5b and c)
towards the matrix (of lower CaO concentration), a signicant por-
that revealed CaCO3 was decomposed between 590 C and 753 C.
tion of the porosity generated at 1100 C was preserved. Besides,
In related systems comprised by a calcined alumina matrix,
the asymmetrical and hexagonal plate-like shape of the CA6 crys-
the decomposition of other inorganic porogenic agents (such
tals also hampered the formation of necking points and reduced
as Al(OH)3 , at 208370 C [3840], Mg6 Al2 (CO3 )(OH)16 4H2 O, at
the densication rate.
200450 C [37], and Mg(OH)2 , at 245406 C [42]) led to an
intense increase in the porosity level, linear shrinkage and reduc-
tion of strength of the structure in comparison to the green
4. Final remarks
samples. Conversely, in the present study, at the same time the
CaCO3 decomposition did not affect signicantly the pore forma-
This paper has addressed an investigation on the pore forma-
tion (Fig. 5a) and thermal dimensional change (Fig. 5b and c),
tion mechanism of in situ calcium hexaluminate (CaO6Al2 O3 or
an early gain of rigidity (Fig. 5a) was observed in comparison to
CA6 ) formed by a thermal treatment (5001500 C) of a compact
the porogenic-free reference sample. Three simultaneous effects
of calcined alumina (-Al2 O3 , the matrix) and calcium carbonate
explain such differences. First, a much lower porogenic agent load
aggregates (CaCO3 , the porogenic agent). The generation of pores
(19.2 vol%, Table 1) was employed in comparison to previous works
was not directly associated with the decomposition of CaCO3 , as
(over 50 vol%, [3740,42]). Second, the CaCO3 clusters (Fig. 2c)
reported for other related systems, such as Al2 O3 -Al(OH)3 and
were formed by rod-like particles poorly packed and containing a
Al2 O3 -Mg(OH)2 . Instead, it is based on interactions amongst the
certain number of inner pores. Therefore, during the thermal treat-
CaO formed after CaCO3 decomposition, alumina particles and
ment, the particles density enhancement and volumetric shrinkage
other calcium aluminates (CA and CA2 ) generated before the total
that follow the CaCO3 decarbonation reaction did not increase the
formation of CA6 .
porosity levels of the samples signicantly (Fig. 4b). Thirdly, the
Due to the pre-existent porosity inside the CaCO3 aggregates,
early rigidity gains are related to the formation of a small portion
their decomposition into CaO (590753 C) did not signicantly
of liquid phase amongst CaO and the impurities of calcined alumina
affect the total level of porosity of the structure up to 900 C.
(especially, Na2 O and SiO2 ).
Above this temperature (samples treated at 11001300 C), a small
amount of liquid phases formed released the inner part of the
3.2. Thermal treatments above 900 C spaces originally occupied by the CaCO3 particles. Due to this, sam-
ples porosity level and strength were simultaneously increased.
Above 900 C, whereas the CaO-free reference samples became SEM/EDS revealed such pores were internally lined with a CaO-rich
denser (Fig. 5a) and more rigid (Fig. 5b), the CaO-containing ones coating (most likely formed by a mixture of CA and CA2 ). At higher
showed a much less intense loss of porosity, linear shrinkage and temperatures (13001400 C), the liquid phase interacts with the
gain of strength. Such opposite behaviors suggest the presence of a surroundings. A further dissolution of alumina changes the com-

Please cite this article in press as: R. Salomo, et al., Mechanism of pore generation in calcium hexaluminate (CA6 ) ceramics formed in situ
from calcined alumina and calcium carbonate aggregates, J Eur Ceram Soc (2016), http://dx.doi.org/10.1016/j.jeurceramsoc.2016.05.026
G Model
JECS-10669; No. of Pages 11 ARTICLE IN PRESS
R. Salomo et al. / Journal of the European Ceramic Society xxx (2016) xxxxxx 9

Fig. 7. Microstructure evolution for C0.0 A6 and C1.0 A samples thermally treated between 1100 C and 1500 C (fracture cross-sections).

position of the system and hexagonal plate-like CA6 crystals are after sintering under the same conditions). The high resistance to
formed around the pores (at 1500 C). densication of such com and simultaneously increased the posi-
Total porosity levels of 40% were attained after sintering at tions was attributed to the volumetric expansion that follows the
1500 C for 3 h (CaCO3 -free reference showed 3% total porosity level formation of calcium aluminates (CA2 and CA6 , particularly) and

Please cite this article in press as: R. Salomo, et al., Mechanism of pore generation in calcium hexaluminate (CA6 ) ceramics formed in situ
from calcined alumina and calcium carbonate aggregates, J Eur Ceram Soc (2016), http://dx.doi.org/10.1016/j.jeurceramsoc.2016.05.026
G Model
JECS-10669; No. of Pages 11 ARTICLE IN PRESS
10 R. Salomo et al. / Journal of the European Ceramic Society xxx (2016) xxxxxx

Fig. 8. EDS mapping of C1.0 A6 samples microstructure after thermal treatment at 11001500 C for 3 h (red = Ca). (For interpretation of the references to color in this gure
legend, the reader is referred to the web version of this article.)

the asymmetric shape of the CA6 grains that intrinsically hampers
the formation of necking points. The maintenance of high-porosity
levels and suitable mechanical properties explain why such CA6
structures are the right raw materials for lightweight refractory
aggregates and suitable candidates for the production of monolithic
porous thermal insulators.
Acknowledgements
The authors acknowledge Brazilian Research Founda-
tions FAPESP (2010-19274-5) and CNPq (470981/2011-3 and
306036/2011-8) for supporting this research and Almatis (Brazil
and Germany) for kindly supplying the samples of calcined
alumina. They are also indebted to P.L. Lorenzo and Prof. Dr.

Please cite this article in press as: R. Salomo, et al., Mechanism of pore generation in calcium hexaluminate (CA6 ) ceramics formed in situ
from calcined alumina and calcium carbonate aggregates, J Eur Ceram Soc (2016), http://dx.doi.org/10.1016/j.jeurceramsoc.2016.05.026
G Model
JECS-10669; No. of Pages 11 ARTICLE IN PRESS
R. Salomo et al. / Journal of the European Ceramic Society xxx (2016) xxxxxx
J.M.D.A. Rollo (SMM/EESC) for the dilatometric analyses and
Electron Microscopy Laboratory of Center for Technology of Hybrid
Materials, CTMH for the SEM images.
References
[1] R.W. Nurse, J.H. Welch, A.J. Majumdar, The CaO-Al2 O3 system in a moisture-free
atmosphere, Trans. Br. Ceram. Soc. 64 (1965) 409419.
[2] D.S. Buist, A study of calcium hexaluminate, Miner. Mag. 36 (281) (1968)
676686.
[3] K.M. Parker, J.H. Sharp, Refractory calcium aluminate cements, Br. Ceram. Trans.
Journal 81 (1982) 3542.
[4] A. Nishikawa, Technology of Monolithic Refractories, Tech. Rept. No 33-7, PLIB-
RICO, Japan, 1984.
[5] A.L. Kelzenberg, S.L. Tracy, B.J. Chrisiansen, J.J. Thomas, M.E. Clarage, S. Hodson,
H. Jennings, Chemistry of the aqueous phase of ordinary Portland cement pastes
at early reaction times, J. Am. Ceram. Soc. 81 (9) (1998) 23492359.
[6] B. Hallstedt, Assessment of the CaO-Al2 O3 system, J. Am. Ceram. Soc. 73 (1)
(1990) 1523.
[7] L.L. Musselman, Production processes, properties, and applications for
aluminum-containing hydroxides, in: L.D. Hart (Ed.), Alumina Chemicals: Sci-
ence and Technology Handbook, The American Ceramic Society, Westerville,
1990, pp. 7592.
[8] S. Jonas, F. Nadachowski, D. Szwagierczak, A new non-silicate refractory of low
thermal expansion, Ceram. Int. 24 (3) (1998) 211216.
[9] D. van Garsel, V. Gnauck, G.W. Kriechbaum, I. Stinneben, New insulating raw
material for high temperature application, in: Proceedings of the 41th Interna-
tionalen Feuerfest-Kolloquium, Aachen, 1998, pp. 122128.
[10] A. Overhoff, A. Buhr, J. Grass, H. Wuthnow, New microporous materials for use
in modern ring plants, Ceram. Forun Int. 82 (8) (2005) E1E5.
[11] R. Kockegey-Lorenz, A. Buhr, R.P. Racher, Industrial application experiences
with microporous calcium hexaluminate insulating material SLA-92, in: Pro-
ceedings of the 48th Internationalen Feuerfest-Kolloquium, Aachen, 2005, pp.
6670.
[12] M. Schnabel, A. Buhr, G. Bchel, R. Kockegey-Lorenz, J. Dutton, Advantages of
calcium hexaluminate in a corrosive environment, Refract.Worldf. 3 (4) (2011)
8794.
[13] D. Asmi, I.M. Low, Physical and mechanical characteristics of in-situ alu-
mina/calcium hexaluminate composites, J. Mater. Sci. Lett. 17 (20) (1998)
17351738.
[14] J. Domnguez, R. Chevalier, T.G. Fantozzi, Microstructure development in cal-
cium hexaluminate, Eur. Ceram. Soc. 21 (2001) 381387.
[15] X. Liu, D. Yang, Z. Huang, S. Yi, H. Ding, M. Fang, S. Zhang, Y. Liu, Novel synthesis
method and characterization of porous calcium hexa-aluminate ceramics, J.
Am. Ceram. Soc. 97 (9) (2014) 27022704.
[16] I.R. de Oliveira, V.M.C. Leite, M.P.V.P. Lima, R. Salomo, Production of porous
ceramic material using different sources of alumina and calcia, Rev. Matr. 20
(3) (2015) 739746.
[17] T. Nagaoka, T. Tsugoshi, Y. Hotta, M. Yasuoka, K. Watari, Forming and sintering
of porous calcium-hexaaluminate ceramics with hydraulic alumina, J. Mater.
Sci. 41 (2) (2006) 74017405.
[18] K. Vishista, F.D. Gnanam, Sol-gel synthesis and characterization of alumina-
calcium hexaluminate composites, J. Am. Ceram. Soc. 88 (5) (2005) 11751179.
[19] Cneyt Ta&#x015F, Chemical preparation of the binary compounds in the
calcia-alumina system by self-propagating combustion synthesis, J. Am. Ceram.
Soc. 81 (11) (1998) 28532863.
[20] M. Gervais Douy, Crystallization of amorphous precursors in the calcia-alumina
system: a differential scanning calorimetry study, J. Am. Ceram. Soc. 83 (1)
(2000) 7076.
[21] V.K. Singh, K.K. Sharma, Low-temperature synthesis of calcium hexa-alumina,
J. Eur. Ceram. Soc. 84 (4) (2002) 769772.
[22] J. Chandradass, D.S. Bae, K.H. Kim, Synthesis of calcium hexaluminate
(CaAl12O19) via reverse micelle process, J. Non-Cryst. Solids 355 (4849)
(2009) 24292432.
[23] L.P. Li, Y. Yan, X.Z. Fan, Z.H. Hu, C.Y. Zhao, Low-temperature synthesis of
calcium-hexaluminate/magnesium-aluminum spinel composite ceramics, J.
Eur. Ceram. Soc. 35 (10) (2015) 29232931.
[24] K. Utsunomiya, H. Tanaka, F.M. Morikawa, Structure renement of CaO6Al2 O3 ,
J. Solid State Chem. 75 (1) (1988) 197200.
[25] C.F. Chan, Y.C. Ko, Effect of CaO content on the hot strength of alumina-spinel
o o
castables in the temperature range of 1000 to 1500 C, J. Am. Ceram. Soc. 81
(11) (1998) 29572960.
[26] M. Fuhrer, A. Hey, W.E. Lee, Microstructural evolution in self-bonding
spinel/calcium aluminate-bonded castable refractories, J. Eur. Ceram. Soc. 18
(7) (1998) 813820.
Please cite this article in press as: R. Salomo, et al., Mechanism of pore generation in calcium hexaluminate (CA6 ) ceramics formed in situ
from calcined alumina and calcium carbonate aggregates, J Eur Ceram Soc (2016), http://dx.doi.org/10.1016/j.jeurceramsoc.2016.05.026
11
[27] E.Y. Sako, M.A.L. Braulio, D.H. Milanez, P.O. Brant, V.C. Pandolfelli, Microsil-
ica role in the CA6 formation in cement-bonded spinel refractory castables, J.
Mater. Process. Technol. 209 (1516) (2009) 55525557.
[28] E.Y. Sako, M.A.L. Braulio, P.O. Brant, V.C. Pandolfelli, The impact of pre-formed
and in situ spinel formation on the physical properties of cement-bonded high
alumina refractory castables, Ceram. Int. 36 (7) (2010) 207920851.
[29] M.A.L. Braulio, G.G. Morbioli, D.H. Milanez, V.C. Pandolfelli, Calcium aluminate
cement source evaluation for Al2 O3 -MgO refractory castables, Ceram. Int. 37
(1) (2011) 215221.
[30] N. Iyi, S. Takekawa, S. Kimura, Crystal chemistry of hexaaluminates: b-Alumina
and magnetoplumbite structures, J. Solid State Chem. 83 (1) (1989) 819.
[31] L. An, H.M. Chan, K.K. Soni, Control of calcium hexaluminate grain morphology
in-situ toughned ceramic composites, J. Mater. Sci. 31 (12) (1996) 32233229.
[32] T. Nagaoka, M. Yasuoka, K. Hirao, S. Kanzaki, Y. Yamaoka, Effects of CaO addition
on sintering and mechanical properties of Al2O3, J. Mater. Sci. Lett. 15 (20)
(1996) 18151817.
[33] J. Jung, S. Baik, Abnormal grain growth of alumina: caO effect, J. Am. Ceram. Soc.
86 (4) (2003) 644649.
[34] J. Domnguez, R. Chevalier, L. Torrecillas, G.F. Gremillard, Thermomechanical
properties and fracture mechanism of calcium hexalumiante, J. Eur. Ceram.
Soc. 21 (7) (2001) 907917.
[35] H. Sarpoolaky, K.G. Ahari, W.E. Lee, Inuence of in situ phase formation on
microstructural evolution and properties of castable refractories, Ceram. Int.
28 (5) (2002) 487493.
[36] W.E. Lee, D.D. Jayaseelan, S. Zhang, Solid-liquid interaction: the key to
microstructural evolution in ceramics, J. Eur. Ceram. Soc. 28 (7) (2008)
15171525.
[37] R. Salomo, M.O.C. Villas-Boas, V.C. Pandolfelli, Porous alumina-spinel ceramics
for high temperature applications, Ceram. Int. 37 (7) (2011) 13931399.
[38] R. Salomo, J. Brandi, Macrostructures with hierarchical porosity produced
from Al2O3-Al(OH)3-chitosan wet-spun bers, Ceram. Int. 39 (7) (2013)
82278235.
[39] A.D.V. Souza, C.C. Arruda, L. Fernandez, M.L.P. Antunes, P.K. Kiyohara, R.
Salomo, Characterization of aluminum hydroxide (Al(OH)3) for its use as a
porogenic agent in castable ceramics, J. Eur. Ceram. Soc. 35 (2) (2015) 803812.
[40] A.D.V. Souza, L.L. Sousa, L. Fernandes, P.H.L. Cardoso, R. Salomo, Al2O3-
Al(OH)3-Based castable porous structures, J. Eur. Ceram. Soc. 35 (6) (2015)
19431954.
[41] L.L. Sousa, A.D.V. Souza, L. Fernandez, V.L. Arantes, R. Salomo, Development of
densication-resistant castable porous structures from in situ mullite, Ceram.
Int. 41 (8) (2015) 94439454.
[42] R. Salomo, A.D.V. Souza, P.H.L. Cardoso, A comparison of Al(OH)3 and Mg(OH)2
as inorganic porogenic agents for alumina, Interceram. Refract. Manual 4 (2015)
193199.
[43] M.A.L. Braulio, V.C. Pandolfelli, Tailoring the microstructure of cement-bonded
alumina-magnesia refractory castables, J. Eur. Ceram. Soc. 93 (10) (2010)
29812985.
[44] T.M. Souza, A.P. Luz, C. Pagliosa, V.C. Pandolfelli, Mineralizing alumina-
magnesia cement-bonded castables containing magnesium borates, Ceram. Int.
41 (9 Part A) (2015) 1114311152, http://dx.doi.org/10.1016/j.ceramint.2015.
05.063.
[45] T. Nagaoka, S. Kanzaki, Y. Yamaoka, Mechanical properties of hot-pressed cal-
cium hexaluminate ceramics, J. Mater. Sci. Lett. 9 (1990) 219221.
[46] L. An, H.C. Ha, H.M. Chan, High-strength alumina/alumina: calcium-
hexaluminate layer composites, J. Am. Ceram. Soc. 81 (12) (1998) 33213324.
[47] B.A. Vzquez, P. Pena, A.H. de Aza, M.A. Sainz, A. Caballero, Corrosion mecha-
nism of polycrystalline corundun and calcium hexaluminate by calcium silicate
slags, J. Eur. Ceram. Soc. 29 (8) (2009) 13471360.
[48] J.M. Tulliani, G. Pags, G. Fantozzi, L. Montanaro, Dilatometry as a tool to study a
new synthesis for calcium hexaluminate, J. Therm. Anal. Calorim. 72 (3) (2003)
11351140.
[49] V.R. Salvini, A.P. Luz, V.C. Pandolfelli, High temperature Al2O3-CA6 insulat-
ing foamed ceramics: processing and properties, Interceram 61 (6) (2012)
335339.
[50] R. Salomo, A.D.V. Souza, L. Fernandes, C.C. Arruda, Advances in nanotechnology
for refractories: when very small meets hot, heavy, and large, Am. Ceram. Soc.
Bull. 92 (7) (2013) 2227.
[51] E. De Guire, Refractoriesengineered, high-performance silent partners, Am.
Ceram. Soc. Bull. 94 (2) (2015) 2627.
[52] C. Henrist, J.P. Mathieu, C. Vogels, A. Rulmont, R. Cloots, Morphological study of
magnesium hydroxide nanoparticles precipitated in dilute aqueous solution, J.
Cryst. Growth 249 (12) (2003) 321330.