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Thermochimica Acta PDF
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, 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
ARTICLE IN PRESS
GModel
TCA-76341; No. of Pages 6
Thermochimica Acta xxx (2013) xxxxxx
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
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, 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. 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
ARTICLE IN PRESS
GModel
TCA-76341; No. of Pages 6
J. Szczerba et al. / Thermochimica Acta xxx (2013) xxxxxx 3
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) [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 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), 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, 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