Cesium Substitution
Cesium Substitution
Cesium Substitution
(aq)
compared to K
(aq)
[18], the amount of hydration water associated
with the Cs was much lower than that with K, so during
continuous heating the mass loss decreased gradually with Cs
content. Over the range from 300 to 600 8C, there was another
weight loss which was attributed to the liberation of water by
condensation/polymerization of SiOH and AlOH groups [8
10]. When temperature further increased, KGP exhibited little
weight change. However, (K
1x
Cs
x
)GP (0 < x _ 0.4) showed
another slow weight loss stage and it was more obvious for
specimens with x > 0.2. The weight loss at this temperature
range might be due to cesium volatization. Because metakaolin
was only partially dissolved in geopolymer (as shown in Section
3.1.3), not all of the alkali cations were bound within the
geopolymer structure. Moreover, it had been reported that
cesium can be easily volatilized from pollucite or analcime at
temperature above 1000 8C [19]. Therefore, on heating, the free
cesium was easily volatilized, leading to the weight loss.
Fig. 1. Weight loss of the as-prepared geopolymer specimens of (K
1x
Cs
x
)GP
measured by TGA from RT to 1300 8C.
P. He et al. / Ceramics International 36 (2010) 23952400 2396
All specimens also exhibit similar DTA thermograms, as
shown in Fig. 2. Two characteristic features were observed from
each thermogram: a large endothermic peak at low temperature
region and a sharp exothermic peak at high temperature region.
The large endothermic peaks in the DTA curves extended from
35 to 300 8C and were attributed to the evaporation of free water
ingeopolymer, as indicatedinthermogravimetric analysis. At the
high temperature region the exothermic peaks were caused by
leucite crystallization, which had been demonstrated in our
recent study. With increasing cesium content from 0 to 0.4, the
exothermic peaks gradually shifted to lower temperatures, i.e.
from1010.3to986.3 8C. Bell et al. [7,8] respectivelyobservedan
exotherm due to leucite and pollucite crystallization from
potassium- and cesium-based geopolymer. In unheated cesium-
based geopolymer there were many small nuclei which served as
the crystallization site for the crystallization. Therefore, as
comparedwithpotassium-basedgeopolymer, onheatingcesium-
based geopolymer wouldcrystallize at a lower temperature. With
increasing cesiumcontent, the number of nucleus would increase
gradually accounting for the measured results in this study.
3.1.2. Dilatometry analysis
Fig. 3 illustrates the variations in the thermal shrinkage of
the (K
1x
Cs
x
)GP (x = 0, 0.1, 0.2, 0.3, and 0.4) with correction.
All specimens exhibited four thermal shrinkage stages, named
as (I) structural resilience, (II) dehydration, (III) dehydroxyla-
tion and (IV) sintering stage. They were consistent with the
observation in a variety of geopolymer, regardless of alkali
choice (Cs, K, and Na) or Si/Al ratio [710].
(1) Stage I extended from approximately 25 to ~ 100 8C.
Minimal shrinkage was observed in all specimens as only
free water from large pores and surfaces was lost in this
stage.
(2) Stage II was over the range of 100 to ~300 8C, and involved
initial stage of rapid thermal shrinkage. Shrinkage in this
stage was due to capillary contraction created when water
was evaporated from the micro- and nano-pores of
(K
1x
Cs
x
)GP.
(3) Stage III occurred over a temperature range from 300 to
700900 8C. The shrinkage in this stage resulted from the
physical contraction of (K
1x
Cs
x
)GP during condensation
reaction from TOH groups to TOT linkages.
(4) Stage IV displayed a signicant thermal shrinkage, which
was due to both skeletal densication and elimination of
large pores by viscous sintering. Large differences in this
stage were observed between these specimens.
In viscous ow sintering, atomic movement occurred by a
cooperative motion mechanismrather than individual diffusion,
and this had been well studied in glasses and solgel materials
[20]. The onset temperature of stage IVoccurred approximately
at 700, 850, 865, 870 and 900 8C for specimens with x = 0, 0.1,
0.2, 0.3, and 0.4, respectively. It indicated that geopolymers
with higher cesium content were more refractory than those
with lower cesium content. Bell et al. [7] reported that cesium-
based geopolymer was much more refractory compared with
potassium- and sodium-based geopolymer and viscous sinter-
ing did not occur until the sample was heated to above 1200 8C.
On the other hand, no eutectic melts with similar composition
of K
(10.7)
Cs
(00.4)
AlSi
2
O
6
were found in the quaternary Cs
2
O
K
2
OAl
2
O
3
SiO
2
system [19]. Thus with increasing cesium
content, the viscosity of the geopolymer gel increased, leading
to the increased onset sintering temperature. It was also
apparent from Fig. 3 that with increasing cesium content
specimens underwent a decreased magnitude of densication,
implying that the barrier to densication was increased greatly
in the presence of cesium, correlating with the increase in
viscosity. The increase in viscosity of geopolymer gel was
likely to be the result of leucite crystallization. Based on the
aforementioned DTA analysis, the crystallization peak temper-
ature decreased as the x increase for 0 _ x _ 0.4, from 1010.3
to 1009.7, 1009.0, 989.8 and 986.3 8C, respectively and stage
IVextended temperature ranges of 700954.3, 850993.7, 865
1004.4, 870997.3 and 9001008.5 8C for specimens with
x = 0, 0.1, 0.2, 0.3, and 0.4, respectively. Crystallization peak
temperatures for specimens with x < 0.3 were higher than the
end temperatures of their respective stage IV. It means that
before specimens was fully densied there was no (for x = 0) or
only a small amount of leucite formed (for x = 0.1, 0.2), which
was benecial for the sintering densication of the specimens.
However, for those with x _ 0.3, crystallization occurred in the
stage IVof thermal shrinkage, which would undoubtedly raise
Fig. 4. Microstructure of (K
1x
Cs
x
)GP before and after heat treatment at 1200 8C for 3 h: (a), (c) and (e) x = 0; (b), (d) and (f) x = 0.3. The write arrows indicate the
partially reacted metakaolin.
P. He et al. / Ceramics International 36 (2010) 23952400 2398
KGP (x = 0). A small amount of cubic leucite was found after
10% Cs
+
ions substituting for K
+
ions (x = 0.1). The intensity of
(4 0 0) peak (2u ~ 26.38) increased with the increment of Cs
content, which indicated the amount of stabilized cubic leucite
increased and with 20% cesium substitution (x = 0.2), leucite
was fully stabilized in cubic phase. No detectable amount of
pollucite was observed in all of the samples.
Taylor [22] and Naray-Szabo [23] had reported that K
+
and
Cs
+
ions occupied the same crystallographic sites (W sites) in
both leucite and pollucite structures. The crystal structure of
pollucite (CsAlSi
2
O
6
) was cubic at room temperature.
Compared with the cesium ion, the smaller size of the
potassiumion (1.66 A
vs. 1.88 A
) to Cs
+
(1.88 A
Fig. 6. Slow step-scan XRD patterns and the calculated lattice parameters of
(K
1x
Cs
x
)GP ceramics: (a) the (4 0 0) peak in a 2u range of 24.528, and (b)
lattice parameters.