Colloids and Surfaces A: Physicochem. Eng.

Aspects 336 (2009) 57–63

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Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Correlating mechanical and thermal properties of sodium silicate-fly

ash geopolymers
John L. Provis ∗ , Chu Zheng Yong, Peter Duxson, Jannie S.J. van Deventer
Department of Chemical and Biomolecular Engineering, The University of Melbourne, Victoria 3010, Australia

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

Article history: The correlation between mechanical and dilatometric properties of aluminosilicate geopolymer binders
Received 22 September 2008 is highlighted by analysis of a set of samples synthesised from a single ash source using different acti-
Received in revised form 6 November 2008 vating solution compositions and liquid/solid ratios. The geopolymers which display the best strength
Accepted 9 November 2008
performance also show a small expansion in the temperature range 700–800 ◦ C, which is identified as cor-
Available online 21 November 2008
responding to the swelling of a high-silica phase present as pockets within the geopolymeric gel structure.
Systems in which this phase is absent (made using hydroxide activating solutions or very low liquid/solid
Keywords:
ratios) generally show a low extent of binder formation and do not achieve high strength, while systems
Geopolymer
Aluminosilicate
in which the expansive phase dominates have a sub-optimally structured geopolymer phase and also
Fly ash correspondingly reduced strength.
Dilatometry © 2008 Elsevier B.V. All rights reserved.
Strength

1. Introduction aluminosilicate gel chemistry obtained by the study of metakaolin

Geopolymeric cements are becoming the focus of increasing
research efforts as the need to reduce global CO2 emissions inten-
sifies. Displaying excellent mechanical strength and resistance
to attack by aggressive environments, these materials represent
an opportunity to simultaneously improve both environmental
and engineering performance compared to traditional technolo-
gies [1,2]. Geopolymers are synthesised by alkaline and/or silicate
activation of a solid aluminosilicate source, resulting in a highly
cross-linked, largely X-ray amorphous gel binder phase bearing
significant similarities to zeolite precursor gels [3]. Geopolymer
synthesis from metakaolin was the focus of much early study [4],
however the possibilities of using coal fly ash as an aluminosilicate
source began to be explored in detail over a decade ago [5,6]. Fly ash
geopolymerisation has since been observed to provide probably the
greatest opportunities for commercial utilisation of this technology
due to the plentiful worldwide raw material supply derived from
coal-fired electricity generation. However, the chemistry of fly ash is
complex [7,8], and so metakaolin geopolymerisation is widely stud-
ied as a ‘model system,’ whereby the relatively simpler chemistry
of the purer system may be used to understand certain aspects of
fly ash geopolymerisation [9]. While there are some significant dif-
ferences in the products obtained from these two different classes
of precursor [10], the ability to use some of the understanding of
∗ Corresponding author. Tel.: +61 3 8344 8755; fax: +61 3 8344 4153.
E-mail address: jprovis@unimelb.edu.au (J.L. Provis).
geopolymers will be of value in this investigation.
Geopolymer synthesis involves a sequence of interdependent
dissolution/reprecipitation reactions, as well as speciation equilib-
ria within the solution phase [11]. These reaction steps are almost
impossible to isolate for individual study, as the process of isolation
of a single step will almost invariably change the reaction conditions
so much that the step of interest either does not occur or plays a
very different role. It is therefore necessary to take a somewhat less
direct approach to the study of specific aspects of geopolymerisa-
tion, and this is where the use of model systems becomes important.
Recent work has provided critical information with regard to the
role played by dissolved silicate speciation in determining geopoly-
mer gel microstructure and kinetics [12–14], and to the respective
roles of different alkali cations in geopolymer gel formation [15–17].
Detailed kinetic studies of both fly ash and metakaolin geopoly-
merisation have shown similar multistep reaction processes, and in
particular the sequential transformation of an initial gel phase into
the final, highly cross-linked gel [18–20]. One of the aims of this
paper is therefore to transfer as much as possible of the knowledge
obtained by systematic studies of metakaolin geopolymerisation to
the more industrially relevant fly ash-based systems. Many workers
have previously published sets of mechanical strength data for fly
ash geopolymers along with some microstructural analysis [21–26].
However, the coupling of mechanical and dilatometric performance
to provide an understanding of binder structure has not previously
been presented.
Dilatometric analysis of metakaolin-based geopolymers has
been undertaken previously [27–32]. In general, a well-reacted

0927-7757/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2008.11.019
58 J.L. Provis et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 336 (2009) 57–63

metakaolin geopolymer shows some initial shrinkage with loss of Table 2

Activator/ash mass ratios (kg activator per kg fly ash) of all samples.
pore water below 300 ◦ C, a period of very gradual shrinkage up to
700 ◦ C associated with dehydroxylation, and then rapid densifica- r m (moles Na2 O/100 g fly ash in r = 0 sample)
tion above this. However, a detailed dilatometric characterisation 0.075 0.100 0.125 0.150 0.175 0.200 0.225
of fly ash geopolymers has not previously been published. Bakharev
0.0 0.195 0.260 0.325 0.390 0.455 0.520 0.626
[33] presented some data showing shrinkage and residual strength 0.5 0.240 0.320 0.400 0.480 0.560 0.641 0.761
of a selection of fly ash geopolymers after heating to 800, 1000 or 1.0 0.285 0.380 0.475 0.571 0.666 0.761 0.896
1200 ◦ C, and Kong et al. [34] discussed the changes in pore struc- 1.5 0.330 0.440 0.551 0.661 0.771 0.881 1.032
ture and residual strength of fly ash geopolymers after heating to 2.0 0.375 0.501 0.626 0.751 0.876 1.001 1.167
800 ◦ C. Kong et al. [35] have also presented a single, low resolu-
tion dilatometric trace for a fly ash geopolymer up to 800 ◦ C, which
shows a sharp shrinkage at ∼200 ◦ C and further shrinkage beyond to the r = 0 sample (determined empirically). This necessitates the
600 ◦ C. Their discussion was focussed on the mismatch between use of slightly increased solution volumes to account for the higher
binder and aggregate behaviour in the geopolymer concretes stud- viscosity of the higher-silica solutions, so that the r = 0.5 sample in
ied, resulting in the increased strength of heated mortar specimens each set had 10% extra solution added, r = 1.0 had 18%, r = 1.5 had
not being reproduced in concretes as the aggregates expanded 24.5% and r = 2.0 had 30%. In the discussions throughout this paper,
while the binder shrank [35]. each set of samples will be referred to by the activator/ash ratio m
The primary aim of this paper is therefore to highlight for the corresponding to the r = 0 sample, but it must be understood that
first time the valuable information that can be obtained by corre- this ratio is only exact for that specific sample within each set.
lating mechanical and dilatometric investigations of geopolymers. The collection of samples tested here spans the entire range in
In terms of determining the strength development of a geopolymer, which a workable, solid geopolymer can be produced from Glad-
there is clearly no substitute for actual strength testing. However, stone fly ash. Ratios below m = 0.075 provide insufficient liquid to
such tests are not always possible where only a small amount of wet the ash, whereas ratios above m = 0.225 do not set. This method
material is available – for example in screening of a large number of of specifying activator/ash ratios provides a more consistent chem-
ash sources, or where a synthetic aluminosilicate precursor is only ical basis for the understanding of fly ash geopolymerisation than
available in small quantities – and so the availability of an alter- would a more traditional mass proportion, because simple mass
native method of analysis may be desirable to provide indicative proportions do not take into account the different solution compo-
measures of strength in such situations. sitions and the need for Na+ to act as a charge-balancing cation in
the aluminosilicate gel structure. For the sake of comparison, the
activator/ash mass ratios of all samples are given in Table 2.
2. Materials and methods
Compressive strength testing was undertaken using mortar
samples, 50 mm cubes, with an ash/sand mass ratio of 0.47. Samples
The work described in this paper utilises fly ash derived from
were cured in moulds sealed into plastic bags with a small amount
a single source, Gladstone Power Station in Queensland, Aus-
of water to maintain a humid atmosphere at 40 ◦ C for 3 days prior
tralia. This is a Class F ash (ASTM C618) with oxide composition,
to strength testing. The results shown are the average of three sam-
determined by XRF, as given in Table 1. Detailed characterisa-
ples, and a mean deviation of <10% was observed where error bars
tion of this fly ash, including identification of the crystalline and
are not shown explicitly. Dilatometry (PerkinElmer Diamond Ther-
non-crystalline phases present, has been presented by Keyte [8].
momechanical Analyser (TMA)) was conducted on hardened paste
The ash contains small quantities of crystalline quartz, mullite,
samples approximately 5 mm in diameter and 10 mm in length,
and iron oxides (hematite/maghemite/magnetite), and is predom-
cured in sealed moulds at 40 ◦ C for 3 days and then stored at
inantly (∼75%) X-ray amorphous. The d50 of Gladstone fly ash is
room temperature for a further 4–7 days. The TMA instrument was
around 10 ␮m, and 5 vol.% of the ash particles are retained on a
operated using a nitrogen purge (i.e. an inert environment in the
45 ␮m sieve.
temperature range of interest) at a flowrate of 200 mL/min and a
Geopolymer samples were prepared by mixing the fly
heating rate of 10 ◦ C/min. X-ray diffractometry (XRD; Philips PW-
ash with sodium silicate activating solutions of composition
1800; Cu K␣ radiation) utilised crushed paste samples.
Na2 O·rSiO2 ·11H2 O, with r = 0, 0.5, 1.0, 1.5 and 2.0. Activator/ash
ratios for each ‘set’ of samples are specified in terms of m, the num-
ber of moles of Na2 O added per 100 g of ash in the sample with r = 0, 3. Results and discussion
and fall in the range 0.075 ≤ m ≤ 0.225. Subsequent samples in each
set, with r = 0.5. . .2.0, are synthesised with comparable workability 3.1. Mechanical strength

Fig. 1 shows a contour plot of compressive strength data for all

Table 1 specimens studied. This plot shows that there is a clear maximum in
Oxide composition of Gladstone fly ash.
mechanical performance in the region 1 ≤ m ≤1.5, 0.125 ≤ r ≤ 0.175.
Oxide Mass % The data for these activator/ash ratios are therefore replotted as
SiO2 46.4
Fig. 2 to enable more detailed analysis.
Al2 O3 28.3 It is of interest to note that the highest strength observed at
Fe2 O3 11.7 each liquid/solid ratio is generated by the use of an activating solu-
TiO2 1.4 tion with r ∼ 1.0–1.5. This corresponds closely to the composition
MnO 0.2
which gives the highest strength in sodium silicate-metakaolin
CaO 5.1
MgO 1.4 geopolymers [12], which was attributed to microstructural details
K2 O 0.6 of the geopolymer gel. In particular, this solution composition gave a
Na2 O 0.3 microstructure that appeared ‘smooth’ and uniform under scanning
P2 O5 1.0
electron microscopy, whereas higher SiO2 /Na2 O ratios gave prod-
SO3 0.3
LOI 3.3
ucts with more obvious unreacted particles, and lower SiO2 /Na2 O
ratios gave a gel microstructure that was clearly particulate and
Total 100.1
porous on a length scale of microns [12]. While there is clearly a
 J.L. Provis et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 336 (2009) 57–63
Fig. 1. Contour plot of compressive strength data for all samples.
significant difference between the geopolymerisation behaviour of
metakaolin and fly ash, due primarily to the different nanostruc-
tures and particle morphologies of these two materials, the fact
that the same activating solution gives the strongest product in
both instances may prove to be of importance. It will be neces-
sary to conduct further analysis on a wider range of fly ash samples
(rather than the single ash tested here) before such correlations
can be attributed to anything more than coincidence, and such
investigations are currently ongoing.
Fig. 2 shows that, as the activator/ash ratio increases, the opti-
mum silicate content of the activating solution decreases. There
is very little difference between the strengths attained at these
three activator/ash ratios using high-silica activating solutions
(m > 1). However, low-silica (and particularly zero-silica, i.e. NaOH)
activators gave significantly higher binder strengths at higher acti-
vator/ash ratios. This is most likely a pH effect; the low-silica
activating solutions have a much higher pH than those with more
SiO2 added. This will mean that the extent of ash dissolution
increases with increasing liquid addition in the lower-silica sys-
tems, as the rate of gel formation in these systems will be strongly
controlled by the kinetics of reactions involving silicate monomers,
and the low-silicate activating solutions contain a very high con-
centration of these species [36]. It has also been observed that
the presence of silicate monomers accelerates fly ash dissolution,
Fig. 2. Compressive strength data for sample sets 0.125 ≤ m ≤ 0.175, where m is the
activator/ash mass ratio of the r = 0 sample in each set.
59
most likely by reducing the reprecipitation of aluminosilicate gel
particles onto the fly ash surfaces [10,37].
Conversely, in the presence of a high-silica activating solution,
there are few silicate monomers present and so the dissolution of
fly ash is relatively slow [10,13]. Coupled with the high degree of
supersaturation with respect to most aluminosilicate phases that
is generated almost as soon as Al starts to dissolve from the ash
into the solution, at least some fraction of the (alumino)silicate
gel phases that form in the higher-Si systems shown in Fig. 2 will
be expected to show a relatively low degree of connectivity when
compared to the generally fully connected structure of the bulk
geopolymer gel. Such less-connected gels have previously been
observed to lead to a rapid expansion upon heating of very high-
silica metakaolin-derived geopolymers [38]. Similar gels, often with
the addition of some alkali metal carbonate (as will be observed in
geopolymers exposed to atmospheric carbonation), are also used
to provide fire resistance to glass laminates due to their significant
swelling upon heating to fire conditions [39]. Expansive behaviour
was therefore expected to be observable by dilatometric analysis
of the fly ash geopolymers investigated here, in the cases where
part of the geopolymer structure consists of a poorly reacted alkali
silicate gel. Non-uniformity of the gel binder has also been pro-
posed as an explanation for some of the unusual behaviour of
low-silica geopolymer systems seeded with small quantities of
alumina nanoparticles [40]. This raises a number of interesting
fundamental questions regarding the definitions of ‘single-phase’
or ‘multi-phase’ in the context of a gel, in the absence of clear
boundaries as are observed in phase-separated glasses, but such
discussion is largely beyond the scope of this work.
3.2. Dilatometric behaviour as a function of solid/liquid ratio
Fig. 3 shows the change in dilatometric performance for geopoly-
mers with r = 1.5, as m is increased from 0.075 to 0.175 (i.e. from
the lowest ratio that was able to be mixed, to the highest ratio
that hardened during curing at 40 ◦ C). The r = 1.5 samples in general
give the highest strengths for each mix ratio m. All samples show
little shrinkage below 100 ◦ C as free water is released (identified
as “Region I” by Duxson et al. [31]), shrinkage from 100 to 250 ◦ C
as pore water is released from the gel (Region II), very gradual (if
any) shrinkage in the range 250–600 ◦ C and attributed to the loss
of bound hydroxyls (Region III), and then, in most cases, densifica-
tion attributed to a process resembling viscous sintering (Region IV)
commencing at around 600 ◦ C. Thermogravimetry (data not shown)
supports the identification of these regions, with the vast majority
of the mass loss taking place below 250 ◦ C in all cases, and attributed
to water loss.
Fig. 3. Dilatometric data for samples with r = 1.5 and varying values of m as marked.
60 J.L. Provis et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 336 (2009) 57–63
Fig. 4. Expansion peak onset and maximum temperatures, and size of expansion peaks, for samples with r = 1.5, as a function of activator/ash ratio.
Fig. 3 also shows that the use of a higher liquid/solid ratio gives
geopolymer products which show a sharp and rapid expansion at
700–800 ◦ C, with the onset temperature decreasing and magnitude
of the expansion increasing with liquid/solid ratio. The higher liq-
uid/solid samples then melt at around 1000 ◦ C. There may also be
effects due to glass devitrification in the presence of alkalis above
800 ◦ C in some samples, but this is difficult to distinguish clearly
in the samples studied. However, the dimensional stability of the
lower liquid/solid samples is quite remarkable, with almost neg-
ligible change in length from 200 to 1000 ◦ C. The geopolymer gel
binder phase is known to be capable of showing very good nanos-
tructural stability up to around 1000 ◦ C [41], and this appears to
be reflected in the dilatometric data for the samples with lower
liquid/solid ratio.
The important parameters of the 700–800 ◦ C expansion peaks
for all samples shown in Fig. 3 are summarised in Fig. 4. The peak
onset is defined as the point at which expansion commences (i.e.
the temperature at which the maximum shrinkage is observed,
immediately prior to the expansion peak), and the height of the
expansion peak is the difference between the length at the onset
temperature and the greatest length measured. Data are not plot-
ted for m = 0.075, as no distinct peak is observed in this sample. The
onset and peak maximum temperatures decrease monotonically,
and the peak height similarly increases, with the addition of more
activating solution to the ash. However, while there is very little dif-
ference between the onset or maximum temperatures for m = 0.15
or 0.175, the peak height changes significantly. This indicates that
the structure of the phase which causes this peak is very similar in
these two samples, but it is present at a higher concentration in the
m = 0.175 sample. This further assists in the association of this peak
with poorly connected silicate gels, possibly derived from pock-
ets of activating solution which are far enough from any reactive
fly ash particle surface that they do not show a significant extent
of Al incorporation. This is not likely to be related to mixing defi-
ciencies; the samples were homogenised using a high-shear mixer,
and mixing problems would be expected to be more notable in the
low-liquid samples which have less favourable rheology. Rather, the
higher liquid/solid ratio, in conjunction with the high viscosity of
the r = 1.5 silicate solution, will mean that there are regions of acti-
vating solution to which dissolved aluminate is unable to diffuse
during the reaction process.
It is also notable here that the samples which show the high-
est strength (m = 0.0125 or 0.015) do show a marked expansion;
it is clear that the presence of the expansive high-silica gel is not
in itself dramatically detrimental to mechanical performance. In
fact, it appears that the best mechanical performance is observed
in the samples which show a slight expansion at above 800 ◦ C—but
whether there is any causation in this relationship (i.e. whether
the expansive gel contributes markedly to mechanical strength)
remains an open question which requires further analysis. It
appears unlikely that this gel does contribute to strength, but rather
that a system which has a sufficiently high liquid/solid ratio to
enable satisfactory conversion of fly ash to geopolymer gel will
result also in the formation of some small amount of this phase.
In the case of metakaolin geopolymers, which have a much higher
level of available aluminium from the solid precursor than do the
fly ash samples tested here, some samples showed a similar expan-
sion peak at around 800 ◦ C superimposed on a very rapid shrinkage
attributed to viscous sintering processes [30,31]. However, this peak
did not appear in a consistent or predictable manner in the data for
metakaolin geopolymers, in contrast to the clear trends observed
here.
Whether the relationship between slight expansion at elevated
and high strength is causative or simply a correlation, the fact that
it exists suggests that dilatometry may be a useful tool in screening
geopolymer mixes and/or ash sources. While it may seem strange to
suggest the use of an instrumental analysis technique as an alter-
native to simple strength testing for screening purposes, the fact
that dilatometry can be conducted on much smaller samples (<1 g
of ash was used per sample tested here, compared to ∼300 g for a
set of three mortar samples for compressive strength testing) may
be an advantage in some instances. In particular, where a sample of
a specific potential aluminosilicate source is to be sent to an exter-
nal laboratory for testing, the ability to obtain results from an easily
transported quantity of a few grams is significantly advantageous.
The use of dilatometry as a method for screening of different fly
ash sources will be explored in detail in a forthcoming publication
[42], making use of the methodology presented and validated in
this paper.
3.3. Dilatometric behaviour as a function of activator composition
Figs. 5–7 present the dilatometric data obtained for the sample
sets with m = 0.125, 0.15 and 0.175 respectively, as a function of sil-
ica content r in each case. Further information regarding the likely
causes of the expansion peak and other features in the dilatometric
traces can be obtained by examination and comparison of these
plots and Fig. 4. For instance, while the data sets in Fig. 4 appear
 J.L. Provis et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 336 (2009) 57–63 61

Fig. 5. Dilatometric data for the sample set with activator/ash ratio m = 0.125 and Fig. 7. Dilatometric data for the sample set with activator/ash ratio m = 0.175 and
varying SiO2 /Na2 O ratios r as marked. varying SiO2 /Na2 O ratios r as marked. Note the change in vertical scale compared to
Figs. 4 and 5.

to show a contraction at a temperature roughly corresponding to

Fig. 6. Dilatometric data for the sample set with activator/ash ratio m = 0.15 and
varying SiO2 /Na2 O ratios r as marked.
the ␣–␤ quartz transition at 573 ◦ C, the r = 0.0 data sets in Figs. 5–7
(which contain the highest mass percentage fly ash, and therefore
the highest remnant quartz content, of all the samples studied)
do not show a corresponding contraction. Cracking of the sample
accompanying this transition is therefore unlikely to contribute to
the observed shrinkage in the samples studied here.
It is also interesting to note that the difference in the magnitude
of the expansion peaks in the high-silica (r ≥ 1.5) samples in the
m = 0.125 and 0.15 sample sets is significantly less than the differ-
ence between the m = 0.15 and 0.175 sets. Adding extra activating
solution to move from m = 0.125 to 0.15 resulted in the formation of
additional geopolymer binder in these samples, meaning that the
added silica did not result in the formation of correspondingly more
of the expansive phase. However, adding more activating solution
to the higher-silica samples led to a decrease in strength (Fig. 2),

Fig. 8. X-ray diffractograms of the sample set with m = 0.175 and r ranging from 0.0 to 2.0. Stick patterns for phases identified are shown below the diffractograms; hematite
peaks overlap with those due to other iron oxides, and the peak resolution was not sufficient to definitively distinguish hydrosodalite from hydroxysodalite, so these phases
are not shown individually.
62 J.L. Provis et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 336 (2009) 57–63
meaning that the extra solution did not lead to the formation of
viable geopolymer binder, and instead gave the expansive silicate
gel. The same is not true for the lower-silica (r ≤ 1.0) activating
solutions; moving from m = 0.15 to 0.175 in these systems gave an
increase in strength, and the expansion peak correspondingly did
not grow markedly.
The X-ray diffractograms presented in Fig. 8 may also pro-
vide some insight into the factors which control the behaviour
of samples synthesised at higher silica content. The identifica-
tion of zeolitic phases in the low-silica samples (chabazite-Na and
hydrosodalite and/or hydroxysodalite in the r = 0.0 sample, and fau-
jasite in the r = 0.5 sample) is consistent across the sample sets with
m = 0.125, 0.15 and 0.175; only the m = 0.175 data are shown here.
It should also be noted that there are multiple Powder Diffraction
File (PDF) entries available for each of these three zeolite structures,
and it was not possible to definitively select a single ‘best’ PDF card
for each phase due to the broad and low-intensity peaks present in
each case. The phases are therefore identified here by framework
type rather than PDF card number.
However, the identification of specific zeolite phases in some
samples is of interest, as it provides a potential explanation for
the differences in behaviour observed at ∼600 ◦ C. The chabazite-
Na phase identified in the r = 0.0 sample is known to convert to
a sodalite framework structure above ∼400 ◦ C [43], with a corre-
sponding decrease in open porosity and thus total volume. The
hydrosodalite/hydroxysodalite (i.e. “non-basic” or “basic” hydroso-
dalite) phases become dehydrated at 400–630 ◦ C, with either a
marked expansion or a small contraction depending on the intra-
cage occupancies of the crystal structure [44]. The small expansion
observed in the r = 0.0 samples in this temperature region may
therefore be tentatively assigned to the expansion of the non-basic
hydrosodalite component of the geopolymer. The slight shrinkage
above 600 ◦ C may then be attributed to restructuring of the gel
and pore network as observed in metakaolin geopolymers previ-
ously [31], along with the dehydration of any basic hydrosodalite
(hydroxysodalite) present, as this is known to be stable to higher
temperatures than its non-basic counterpart.
The r = 0.5 samples show the formation of faujasite as the only
significant zeolite phase. The structural collapse of faujasite has pre-
viously been identified in differential thermal analysis (DTA) data
for metakaolin-based geopolymers, but did not give a significant
peak in dilatometry [31]. These, and the r = 1.0 and 1.5 phases which
do not show notable zeolitic crystallinity, begin to shrink notably at
∼600 ◦ C prior to the onset of the expansion peak at ∼700–800 ◦ C.
The r = 2.0 samples do not actually show a clear shrinkage prior
to the onset of expansion, however this may be attributed to the
early and rapid onset of the expansion of the high-silica phase
overwhelming the shrinkage of the remainder of the gel phase.
4. Conclusions
The correlation between mechanical and dilatometric perfor-
mance of sodium silicate-fly ash geopolymers has been identified,
and rationalised in terms of the expansion of a high-silica phase
which comprises part of the gel binder in samples with high levels of
activating solution addition, or very high-silica activating solutions.
Samples which show either a very large or a negligible expansion in
the temperature range 700–800 ◦ C do not generally show the high-
est strengths; optimal mechanical performance is provided by the
mixes which show a small expansion in this temperature range. It
is believed that this trend is due to a correlation of physical proper-
ties rather than being a strictly causative effect—i.e., the expansive
phase is not directly responsible for high strength development, but
remains as pockets in the geopolymer binder structure as a result
of the high activating solution viscosity and relatively high solution
content of the geopolymers which show the highest strength. The
use of dilatometry provides a method of screening potential pre-
cursors for geopolymerisation, which may prove more convenient
than the synthesis of larger samples for mechanical strength testing
in cases where the transport of large quantities of materials proves
problematic.
Acknowledgments
This work was funded in part by the Australian Research Council
(ARC), including funding through the Discovery Grants program and
also via the Particulate Fluids Processing Centre, a Special Research
Centre of the ARC.
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