Please cite this article in press as: J. Szczerba, et al.

, The application of DTA and TG methods to investigate the non-crystalline hydration products
of CaAl
2
O
4
and Ca
7
ZrAl
6
O
18
compounds, Thermochim. Acta (2013), http://dx.doi.org/10.1016/j.tca.2013.01.031
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Contents lists available at SciVerse ScienceDirect
Thermochimica Acta
j our nal homepage: www. el sevi er . com/ l ocat e/ t ca
The application of DTA and TG methods to investigate the non-crystalline
hydration products of CaAl
2
O
4
and Ca
7
ZrAl
6
O
18
compounds
Jacek Szczerba

, Dominika Madej, Edyta

Snie zek, Ryszard Prorok
AGH University of Science and Technology, Faculty of Materials Science and Ceramics, al. A. Mickiewicza 30, 30-059 Krakow, Poland
a r t i c l e i n f o
Article history:
Available online xxx
Keywords:
Hydration
DTATGAEGA methods
CaAl
2
O
4
Ca7ZrAl
6
O
18
Calciumaluminate hydrates
Microstructure
a b s t r a c t
The hydration products and thermal decomposition mechanism of hydrated CaAl
2
O
4
and Ca
7
ZrAl
6
O
18
compounds were investigated by X-ray diffraction, SEM/EDS and thermal analysis. The processes of crys-
tal hydrate nucleation and precipitation were preceded by the evolution of the X-ray amorphous phase
during the rst 24h of hydration. DTATGAEGA techniques allowed the study of the detailed decom-
position and identication of intermediate and stable to be performed. The differential thermal analysis
(DTA) curves of hydrated CaAl
2
O
4
and Ca
7
ZrAl
6
O
18
compounds show ve similar endothermic peaks due
to crystal water desorption. According to the quantitative TGAEGA analyses performed on hydrated
CaAl
2
O
4
and Ca
7
ZrAl
6
O
18
compounds, it was found that C
2
AH
8
, C
3
AH
6
and Al(OH)
3
phases are the main
hydration products of CaAl
2
O
4
. Under the same laboratory conditions, the hydration of Ca
7
ZrAl
6
O
18
pro-
ceeds with the formation of mainly CAH
10
and AH
3
-gel phases. We provide the original illustrations of
the hydrate crystals formation via amorphous phases.
2013 Elsevier B.V. All rights reserved.
1. Introduction
Calcium aluminate cements (CACs) constitute an important
component of monolithic refractory materials. CACs consist
predominantly of hydraulic calciumaluminates. Calciummonoalu-
minate CaAl
2
O
4
(CA; C=CaO, A=Al
2
O
3
) is the principal cementing
compound in CACs with the incongruent melting point at 1602

C
[1]. Two calcium aluminate hydraulic phases: CaAl
4
O
7
and
Ca
12
Al
14
O
33
(CA
2
and C
12
A
7
) are the minor components.
The hydration of aluminates, such as CaO Al
2
O
3
compounds,
is a highly temperature and time dependent process. Hexagonal
calcium aluminate hydrates: CAH
10
, C
2
AH
8
and C
4
AH
19
(H=H
2
O)
as the main products at low temperatures that transformbecause
of a higher temperature (>40

C) into the stable hydrogarnet C

3
AH
6
and AH
3
phases [24].
As it has been reported [5,6], calcium zirconium aluminate,
Ca
7
ZrAl
6
O
18
(C
7
A
3
Z; Z=ZrO
2
) is the only zirconiumcontaining the
aluminate phase which simultaneously exhibits all the hydraulic
properties. The ternary compound was found to melt incongru-
ently at 1550

C with a formation of solid calciumzirconate CaZrO

3
and a liquid [7]. The hydraulic activity of Ca
7
ZrAl
6
O
18
suggested
its potential application in conjunction with CaAl
2
O
4
in the new
shaped and unshaped refractories. For this reason, in this paper we

Corresponding author. Tel.: +48 12 617 25 01.

E-mail address: jszczerb@agh.edu.pl (J. Szczerba).
investigate the thermal decomposition mechanismof CaAl
2
O
4
and
Ca
7
ZrAl
6
O
18
compounds.
As a consequence of poor crystallinity of hydration products
formed after the addition of water for hydraulic setting of the cal-
cium aluminate cement at the early hydration stage, the phase
identicationbyXRDis difcult. Inthis regard, the differential ther-
mal analysis (DTA) combined with the thermogravimetric analysis
(TGA) and the evolved gas analysis (EGA) play an important role in
qualitative and quantitative investigations.
The effect of a heat treatment on hydrated calcium alumi-
nate cement paste and the calcium aluminate minerals (CaAl
2
O
4
,
CaAl
4
O
7
, Ca
12
Al
14
O
33
) have been extensively studied in the past
[818] by measuring the weight and thermal effects of speci-
mens as they undergo heating. Alarcon-Ruiz and Harmathy [8,19]
explain that during the cement paste heat treatment, a con-
tinuous sequence of more or less irreversible decomposition
reactions take place. Previous work [15] summarized the results
of the thermal analysis of the binary and ternary compounds in
the CaO Al
2
O
3
H
2
O system. This approach offers the advantage
to study both the mass losses and characteristic temperatures
(DTA endothermic peaks) obtained from TGA and DTA curves,
respectively. Differential thermal and thermogravimetric analysis
(DTA/TGA) are widely used in evaluating the hydration products
cement pastes [8]. These techniques are based on assumption that
decomposition of a starting material occurs within a xed temper-
ature range. Water vapour is given off resulting in weight change
of the test sample. Therefore, it may be simply concluded from
this data that the qualitative and quantitative identications of
0040-6031/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.tca.2013.01.031
Please cite this article in press as: J. Szczerba, et al., The application of DTA and TG methods to investigate the non-crystalline hydration products
of CaAl
2
O
4
and Ca
7
ZrAl
6
O
18
compounds, Thermochim. Acta (2013), http://dx.doi.org/10.1016/j.tca.2013.01.031
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Table 1
Specication of the starting materials.
Specication Reagent
CaCO
3
(Chempur)
Al
2
O
3
(Chempur)
ZrO
2
(Merck)
Pure (%) 98.81 98.50 98.08
Median particle size (m) 2.303 36.229 20.762
Specic surface area (m
2
/g) 3.09 0.357 0.306
the hydrated compounds known to decompose within dened
temperature ranges can be done. Moreover, the exothermic peaks
on the DTA curve can be attributed to the crystallization of new
phases. The aimof this work was to recognize and compare of main
hydration products of CaAl
2
O
4
and Ca
7
ZrAl
6
O
18
based on ther-
mal analysis andscanningelectronmicroscopy. The DTATGAEGA
results of hydratedCaAl
2
O
4
andCa
7
ZrAl
6
O
18
compounds accompa-
nied with microstructure observations led to extensive discussions
onthe type andcrystal habit of calciumaluminate hydrates present
in the hydrating pastes.
2. Experimental
2.1. Materials and methods
The standard solid state reaction method was used to syn-
thesize CaAl
2
O
4
(CA sample) and Ca
7
ZrAl
6
O
18
(C
7
A
3
Z sample). In
case of the CaAl
2
O
4
pure chemical CaCO
3
and Al
2
O
3
were mixed
together in the proportion of the CaO to Al
2
O
3
ratio corresponding
to the CaAl
2
O
4
stoichiometry. Ca
7
ZrAl
6
O
18
was synthesized from
a stochiometric mixture composed of CaCO
3
, Al
2
O
3
and ZrO
2
. The
specication of the starting materials is shown in Table 1.
The mixtures were homogenized by milling with zirconia balls
for 2h. Subsequently, the specimens were formed as cylinders with
diameter and height of 20mm. The reactions of the CaAl
2
O
4
and
Ca
7
ZrAl
6
O
18
synthesis were carried out by the two step ring pro-
cedure. First, the samples were calcined at 1200

C for 10h. After

this stage, the samples were ground to the grain size lower than
63m and again pressed into discs under a pressure of 120MPa.
Consequently, the samples were sintered at 1500

C with 10h (CA

sample) or 30h (C
7
A
3
Z sample) soaking time and cooled with the
furnace.
The powder X-ray diffraction was adopted in the present study.
PANalytical XPert Pro MPD with a Cu K radiation was used. The
polished fractures of sinters, produced at 1500

C, were observed
under a scanning electron microscope (SEM) and analyzed by
energy dispersive X-ray spectroscopy (EDS). The ultra high de-
nition NOVA NANO SEM 200 was used for this purpose. As a next
step, the synthesized samples were ground and then their specic
surface and grain size distribution was measured by a laser diffrac-
tion analyzer (the Mastersizer 2000 Ver. 5.60 apparatus of Malvern,
UK). Hydrated CA and C
7
A
3
Z pastes were prepared with a water
to solids ratio of 0.50. The size of the CA and C
7
A
3
Z samples was
5g, respectively. The room temperature was 20

C and humidity
above 80%. Powders and water were mixed together by hand in a
sealed plastic bag for 35min. The hardened CA and C
7
A
3
Z pastes,
which were left at room temperature for 24h, were observed
under SEM after the experiment. The samples were ground and
the reaction was stopped by cold acetone. The use of acetone, aim-
ing to withdraw free water and inhibit further reactions is known
from the literature [20]. Simultaneous differential thermal and
thermogravimetric analyses with gas emission (DTATGAEGA)
were performed with a SDT 2960 type STA (Simultaneous Thermal
Analyzer) of TA Instruments (TG, DTG, DTA, QMA) at a heat-
ing rate of 10

C/min. The samples with of 54.33mg (hydrated

CA) and 42.41mg (hydratedC
7
A
3
Z) masses were placed in the
Fig. 1. Measured powder XRD pattern of (a) single phase CaAl
2
O
4
(unhydrated CA
sample) and (b) hydrated CA sample.
corundum crucibles and heated from room temperature up to
1150

C. 100.00mg of Al
2
O
3
was used as the reference substance.
The phase composition of hydrated CA and C
7
A
3
Z samples was
examined by powder diffraction.
3. Results and discussion
3.1. Phase composition and microstructure of CA and C
7
A
3
Z
materials before the hydration process
The initial materials, sintered at 1500

C, are CaAl
2
O
4
and
Ca
7
ZrAl
6
O
18
. The measured diffraction patterns of CA and C
7
A
3
Z
samples are presented in Figs. 1a and 2a, respectively. In both cases
there is no signicant evidence of existence of secondary phases on
the measured XRD patterns. With the exception of the C
7
A
3
Z sam-
ple, which contains some amount of accessory CaZrO
3
(Fig. 2a), the
Fig. 2. Measured powder XRD pattern of (a) single phase Ca7ZrAl
6
O
18
(unhydrated
C7A
3
Z sample) and (b) hydrated C7A
3
Z sample.
Please cite this article in press as: J. Szczerba, et al., The application of DTA and TG methods to investigate the non-crystalline hydration products
of CaAl
2
O
4
and Ca
7
ZrAl
6
O
18
compounds, Thermochim. Acta (2013), http://dx.doi.org/10.1016/j.tca.2013.01.031
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Fig. 3. SEMimage of the CAsample microstructure after 10h of sintering at 1500

C.
(Spot 1) EDS analysis: 1 CaAl
2
O
4
.
SEMobservations revealed the presence of well developed CaAl
2
O
4
andCa
7
ZrAl
6
O
18
grains (Figs. 3and4). The explanationis conrmed
by EDS analyses, shown in Figs. 3 and 4 Spots 1.
3.2. Particle size distribution of CA and C
7
A
3
Z samples
Grain size distributions of powdered CA and C
7
A
3
Z samples are
characterized by the medians (d
0.5
) and correspond to 36.134m
(specic surface of 0.381m
2
/g) and 29.743m (specic surface
of 0.475m
2
/g), respectively. The samples revealed rather broad,
mono-modal grain size distributions (Fig. 5). The results of spe-
cic surface area of the CA sample were similar to the results of the
C
7
A
3
Z sample.
3.3. Phase composition and microstructure of CA and C
7
A
3
Z
materials after the hydration process
The CA and C
7
A
3
Z samples exhibited high background inten-
sity (Figs. 1b and 2b) indicating that the hydrated CaAl
2
O
4
and
Ca
7
ZrAl
6
O
18
contained a proportion of highly disordered mate-
rials in the form of amorphous calcium aluminate hydrates
(xCaOyAl
2
O
3
zH
2
O). The effect of amorphous materials on the
broadening of the XRD patterns of the hydrated CA and C
7
A
3
Z
pastes is not negligible.
Three crystalline components of the hydrated CA paste were
found by XRD: the initial unhydrated material, i.e. CaAl
2
O
4
, and
Fig. 4. SEM image of the C7A
3
Z sample microstructure after 30h of sintering at
1500

C. (Spot 1) EDS analysis: 1 Ca7ZrAl

6
O
18
.
the newly created phases, i.e. Al(OH)
3
and C
4
AH
19
(Fig. 1b). More-
over, the unidentied peaks in the XRD pattern (Fig. 1b) should
represent the still remaining hydrated CaAl
2
O
4
crystals or crys-
tal nuclei for synthesizing calciumaluminate hydrates, rather than
Fig. 5. The particle size distribution in the CA and C7A
3
Z powder samples.
Please cite this article in press as: J. Szczerba, et al., The application of DTA and TG methods to investigate the non-crystalline hydration products
of CaAl
2
O
4
and Ca
7
ZrAl
6
O
18
compounds, Thermochim. Acta (2013), http://dx.doi.org/10.1016/j.tca.2013.01.031
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Fig. 6. (a and b) Microstructure of hydrated CA sample.
well-cristallizedcalciumaluminatehydrates [21]. Theternarycom-
pounds of the CaO Al
2
O
3
H
2
O system (with the exception of
C
4
AH
19
), not found in the XRDpattern (Fig. 1b), appear as an amor-
phous substance.
Three crystalline components of the hydrated C
7
A
3
Z paste were
found by XRD: the initial unhydrated Ca
7
ZrAl
6
O
18
, CaZrO
3
and
C
4
AH
19
(Fig. 2b). Other hydrates of calcium aluminates (CAH
10
,
C
2
AH
8
, C
3
AH
6
), not found in the XRD pattern (Fig. 2b), appear as
an amorphous substance in C
7
A
3
Z paste. It can be concluded that
the increased intensity of the CaZrO
3
peak in the hydrated sam-
ple could be ascribed to the formation of additional amounts of
CaZrO
3
. In the initial, unhydrated C
7
A
3
Z sample this phase occurs
in a negligible amount, and can be treated as an impurity. The rel-
ative intensity of the CaZrO
3
peak corresponding to d=2.83600 in
the C
7
A
3
Z sample was 4.85% before hydration (Fig. 2a). It rose up
to 13.17% after hydration (Fig. 2b).
Figs. 6a, band7ac showthe SEMmicrostructure of hydratedCA
andC
7
A
3
Z samples, respectively. It canbe seenfromthe SEMimage
that partially hydrated grains of CaAl
2
O
4
(Fig. 6a) and Ca
7
ZrAl
6
O
18
(Fig. 7a) still contain unhydrated cores. The reaction proceeds as
the CaAl
2
O
4
and Ca
7
ZrAl
6
O
18
grain cores are consumed.
SEM observations show that hydration products of aluminate
phases had an amorphous structure rather than a well-crystallized
structure. Nevertheless, some crystal nuclei for synthesizing
calcium aluminate hydrates are observed under higher magni-
cation (Figs. 6b and 7b). After the formation of these crystallization
nuclei, a massive precipitationis most likely to occur during a time-
dependent hydration process. The presence of the stable hydrate
C
3
AH
6
in the formof a semicubic or spherical shape can be identi-
ed (Fig. 6b) which has also been reported by Das et al. [22]. Some
of these crystals, such as hexagonal calcium aluminium hydrates
(CAH
10
, C
2
AH
8
, C
4
AH
19
), can be also detected (Fig. 6b). However,
the SEM observations indicate that the CA sample still contains a
quite large amount of the unstable amorphous phase (Fig. 6a and
b).
The SEMobservations showed that the hydrated C
7
A
3
Z sample
containeda lamellar amorphous phase or other more irregular ones
(Fig. 7a). The hydrated product of the Ca
7
ZrAl
6
O
18
compound in a
grain of C
7
A
3
Z sample adheres rmly to the unhydrated core of the
grains of the C
7
A
3
Z sample.
Fig. 7b shows the scanning electron microscope (SEM) image
under a higher magnication of the plate-like crystal morphol-
ogy of the hydrated Ca
7
ZrAl
6
O
18
phase. This indicates the calcium
aluminate hydrates crystallization from the amorphous phase.
Hexagonal-plate morphology is the characteristic feature of CAH
10
,
which has also been reported by Parr [23]. Moreover, as it can
be seen in Fig. 7c, hydration of Ca
7
ZrAl
6
O
18
compound pro-
ceeds with the formation of nely crystalline (light spots) CaZrO
3
(T
mp
=2345

C) [24,25].
3.4. The DTATGAEGA investigation of hydrated CA and C
7
A
3
Z
samples
The DTATGAEGA measurements show that the thermal
decomposition of partially hydrated CaAl
2
O
4
occurs in several
steps (Figs. 8 and 9). In this process, amorphous calcium alumi-
nate hydrates break down to water vapour and solid phases start
to form. A DTA curve of hydrated CaAl
2
O
4
shows ve endothermic
peaks with the maxima at 97.94

C, 165.93

C, 285.48

C, 451.29

C
and 548.42

C, respectively (Fig. 8, Table 2). It is shown that these

endothermic maxima in the DTA curve correspond to the mass loss
due to the release of H
2
O in the TG curve (see the EGA curve
Fig. 9, CA sample) [8]. The rst step occurs up to 97.94

C and it is
attributed to the dehydration process of CAH
10
and AH
3
-gel [10,26]
and a 4.35% mass loss as shown by the thermogravimetric curve
(Fig. 8).
The second small endothermic peak appears at 165.93

C and
represents the loss of water (see the EGA curve Fig. 9, CA sample)
due to further dehydration of CAH
10
[16]. On the other hand, this
temperature is close to the temperature value of C
2
AH
8
decompo-
sition, estimated by George [26]. Hence, it can be concluded that
the presence of both CAH
10
and C
2
AH
8
cannot be excluded. This
endothermic peak position corresponds to the 3.66% mass loss on
the TG curve (Fig. 8).
At 285.48

C, the third step of hydrated paste decomposition

is accompanied by a sharp endothermic DTA peak (Fig. 8) and a
9.66% mass loss, as shown by the thermogravimetric curve (Fig. 8).
This could be attributedto the thermal decompositionof the C
2
AH
8
residueandtothesubsequent decompositionof C
3
AH
6
andAl(OH)
3
during heating period [16,27]. The EGA curve of the CA sample
(Fig. 9) shows the release of H
2
O (maximum at 285.48

C), indi-
cating that the C
2
AH
8
, C
3
AH
6
and Al(OH)
3
phases are degraded at
this stage (see Table 2).
The fourth endothermic peak appears at 451.29

C in this sam-
ple with a weight loss of 6.81% which is attributed to the water loss
in the solid (Fig. 8). This could be attributed to the thermal decom-
position of C
3
AH
6
residue. Besides, the C
4
AH
19
hydrate starts to
decompose at this temperature [2].
The last mass loss (1.02%), corresponding to the endothermic
peaks at 548.42

C, is attributedtothethermal decompositionof the

Please cite this article in press as: J. Szczerba, et al., The application of DTA and TG methods to investigate the non-crystalline hydration products
of CaAl
2
O
4
and Ca
7
ZrAl
6
O
18
compounds, Thermochim. Acta (2013), http://dx.doi.org/10.1016/j.tca.2013.01.031
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Fig. 7. (ac) Microstructure of hydrated C7A
3
Z sample.
Ca(OH)
2
residue (see Fig. 8 and Table 2). The differential thermal
curve shows only one exothermic peak at 954.22

C, presumably
corresponding to the crystallization of calcium aluminates (C
12
A
7
or CA) (see Fig. 8 and Table 2).
As it was reported previously [6], the hydrated C
7
A
3
Z sam-
ple is characterized by endothermic peaks on the DTA curve. Five
dehydration weight loss steps were observed for the hydrated
Fig. 8. DTATGA curves of CA hydrated paste.
Ca
7
ZrAl
6
O
18
compound at 88.43

C, 159.78

C, 261.67

C, 439.20

C
and 534.35

C (see Table 2). As it can be seen from Table 2, they

are in good agreement with the endothermic effects during heat-
ing of the hydrated CA sample, which were also attributed to the
dehydration of calcium aluminate hydrates. It is known that the
higher crystallization of calciumaluminate hydrates results in the
endothermic peaks shifted to higher temperatures in the case of
CaAl
2
O
4
after the hydration process (hydrated CA sample). A max-
imum endothermic peak (88.43

C) related to the dehydration of

Fig. 9. EGA curves of CA and C7A
3
Z hydrated pastes.
Please cite this article in press as: J. Szczerba, et al., The application of DTA and TG methods to investigate the non-crystalline hydration products
of CaAl
2
O
4
and Ca
7
ZrAl
6
O
18
compounds, Thermochim. Acta (2013), http://dx.doi.org/10.1016/j.tca.2013.01.031
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Table 2
Comparison of DTA peaks of CA and C7A
3
Z samples.
CA sample C7A
3
Z sample [6] Phases
Temperature (

C) Mass loss (%) Temperature (

C) Mass loss (%)

Endothermic effects
97.94 4.35 88.43 6.85 CAH
10
, AH
3
-gel
165.93 3.66 159.78 6.36 CAH
10
, C
2
AH
8
285.48 9.66 261.67 5.79 C
2
AH
8
, C
3
AH
6
, Al(OH)
3
451.29 6.81 439.20 6.64 C
3
AH
6
, C
4
AH
19
548.42 1.02 534.35 0.95 Ca(OH)
2
Exothermic effects
954.22 907.06 Crystallization of
calciumaluminates
C CaO; A Al
2
O
3
; H H
2
O
the CAH
10
, AH
3
-gel, was assisted by the evolution of water vapour
(EGAcurve inFig. 9). What is more, the ioncurrent signals are much
weaker than those obtained for the CA sample.
4. Summary and conclusions
From the above ndings, it can be concluded that the semi-
crystalline to nearly amorphous and thin layers of the calcium
aluminate hydrates, i.e. CAH
10
, C
2
AH
8
, C
3
AH
6
and C
4
AH
19
which
cover the initial CaAl
2
O
4
and Ca
7
ZrAl
6
O
18
grains can moderate the
reaction rate of the aluminate phases by reducing the diffusion of
water in the direction of the aluminate phases grain cores. Nev-
ertheless, the hydration proceeds as the hydration shells thicken
and consume the CaAl
2
O
4
and Ca
7
ZrAl
6
O
18
grain cores. An impor-
tant microstructural aspect of the early hydration of CaAl
2
O
4
and
Ca
7
ZrAl
6
O
18
compounds is the formation of a shell of hydration
products around the aluminate grains. The occurrence of the ther-
modynamically stable C
3
AH
6
and AH
3
phases in the CA and C
7
A
3
Z
samples indicate partial transformation of the unstable calcium
aluminate hydrates (CAH
10
, C
2
AH
8
, C
4
AH
19
) at roomtemperature.
Thesharpendothermic peaks ontheDTAcurves areassociatedwith
decomposition of these hydrates. The TGA curves of the CA and
C
7
A
3
Z pastes showed a ve-step water loss, including four effects
for calciumaluminate hydrates. The decompositionof the hydrates,
i.e. CAH
10
, C
2
AH
8
and C
3
AH
6
, proceeds via two stages causing the
two thermal effects for each compound but these DTA peaks coin-
cide with each other. Therefore, it can be concluded from this
data that the qualitative identication of the hydrated compounds
knowntodecompose withindenedtemperature ranges was done.
Moreover, it was found that C
2
AH
8
, C
3
AH
6
and Al(OH)
3
phases are
themainhydrationproducts of CaAl
2
O
4
. Under thesamelaboratory
conditions, the hydration of Ca
7
ZrAl
6
O
18
proceeds with the forma-
tion of mainly CAH
10
and AH
3
-gel phases. The sharp endothermic
peaks give evidence that hydrates possess some degree of crys-
talline order but at early stages of hydration they are not detectable
on X-ray yet.
Acknowledgement
This work is supported by the grant no. N N507 45 76 37 of the
Polish Ministry of Science and Higher Education.
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