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geopolymers can then be described as Newtonian uids with the viscosity controlled mainly by the high
viscosity of the suspending alkaline silicate solution and not by the contribution of direct contacts
between metakaolin grains. This fundamental dierence between geopolymers and OPC implies that
DOI: 10.1039/c3sm51889b
developments made in cement technology to improve rheological behaviour such as plasticizers will not
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be ecient for geopolymers and that new research directions need to be explored.
1. Introduction
The fundamentals behind the visco-elastic properties of
concentrated solid suspensions have been a subject of study for
many years.1 Beyond scientic curiosity, this interest has been
driven by the prevalence of concentrated suspensions in many
industrial formulations. Among them, the cementitious paste
used to cast concrete in the building industry is arguably by far
the most used today in volume.2 As a consequence, the so
matter properties of fresh Ordinary Portland Cement (OPC)
pastes have been the subject of particular attention since the
late 80's.3 It so happens that OPC pastes and OPC-based
concrete, despite being common and seemingly dull construction materials, actually hide a complex and challenging rheological behaviour that has only been grasped by combining the
knowledge of three disciplines: colloidal physics, inorganic
chemistry and uid mechanics.4
Indeed, signicant practical advances such as the development of self-compacting concretes5 able to ow under the sole
eect of gravity, high-mechanical strength concretes6 able to
ow while having a solid volume fraction higher than 90% or
bre-reinforced concretes7,8 able to ow while containing
elongated rigid steel bres were only possible because of
fundamental questioning of granular paste rheology.9
a
(1)
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2.
Experimental procedure
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Table 1
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Geopolymer paste
SiO2/Na2O (solution)
H2O/Na2O (solution)
1.15
15
1.8
3.
Fig. 1
dominated over the contributions of both the colloidal interactions and particle inertia over a larger range of shear rates
than in the case of cement pastes.
3.2. Evaluation of the colloidal contribution to the yield
stress
We then extrapolated the yield stress s0 from shear stress
measurements in the low shear rate range. In Fig. 3, the
evolution of shear stress for cement paste, geopolymer and
geopolymer constitutive silicate solutions is shown as a function of shear rate. Table 2 gives the estimated values of shear
stresses. Obviously, compared to the cement and MK suspensions, the silicate solution could be considered as a purely
viscous uid as its yield stress is between one and two orders of
magnitude lower than that of the cement paste (Fig. 3). The
yield stress could be fully neglected compared to the contribution of viscous dissipation to the shear stress. The viscosity of
the silicate solution being almost constant, it behaved similarly
to the interstitial water in the cement paste also shown in Fig. 3
and can be described as a Newtonian uid.
Moreover, we measured the onset of ow as a function of the
shear strain for both the standard OPC paste and MK paste
using a vane test procedure.34 Let us recall that in this test, the
sample is sheared at a very low shear rate and the evolution of
stress with shear strain is recorded. Fig. 4 shows the result of
this vane test for cement and geopolymer pastes.
Fig. 4a shows results typical of a cement suspension. It
displays two characteristic critical strains. The rst one is
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Shear stress as a function of shear rate for geopolymer (H2O/Na2O 15; f 0.3), cement paste (W/C 0.35 and f 0.47), the geopolymer suspending uid (silicate solution) and the cement suspending uid.
Fig. 3
Yield stress
Geopolymer paste
Standard cement paste
Sodium silicate solution
Cement interstitial uid
2 Pa
20 Pa
0.01 Pa
0.001 Pa
around 103 whereas the second one is between 102 and 101.
Recent studies have shown that the peak associated with the
smallest critical strain nds its origin in the breaking of
the calcium silicate hydrates (CSH) percolating between the
cement grains. The second peak nds its origin in the collapse
of the colloidal interaction network.35 Above this second critical
strain, the system is considered to be owing. In the geopolymer
system though, we observed only one peak (Fig. 4b). It was
located between 102 and 101. This suggests that only one type
of interaction between particles is involved, and that once the
particles have moved suciently far from their initial positions,
this interaction vanishes and the ow starts. Recently, Favier
et al.36 have shown that the elastic modulus observed in the MKbased geopolymer is due to the formation of an inter-grain gel at
a very early stage and is not due to colloidal interactions
between grains. They observed that the critical strain of a geopolymer (as shown in Fig. 4b) is controlled by the critical strain
of an inter-grain aluminosilicate gel. As a consequence, geopolymer pastes seem to have their yield stress controlled solely
by the percolation of an aluminosilicate gel between MK particles, and no colloidal interactions between MK particles are
involved.
Furthermore, as already observed above, geopolymers have a
yield stress far lower (<0.1 Pa) than that of typical cement paste
(>10 Pa). This suggests that the attraction between CSH is
much stronger than the cohesion of the early aluminosilicate
gel produced in the early stages of the geopolymeric reaction.
From these dierences, an important practical consequence
can be anticipated. As the role of cement rheology modifying
industrial admixtures is to reduce the yield stress by minimizing colloidal interactions between particles, such admixtures would be of no eect for geopolymer pastes since their
yield stress is not related to colloidal interactions but to the
percolation of the early reaction products.
3.3. Evaluation and comparison of the viscosities of fresh
cement and geopolymer pastes
Fig. 4 Vane test experiments (a) for the standard cement paste plotted
from (N. Roussel et al. 2012) (W/C 0.4 and f 0.44) after 20 minutes
and (b) for the geopolymer paste (H2O/Na2O 15, f 0.3) after 10
minutes at room temperature.
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Solution viscosity
Solid fraction
Water 0.001 Pa s
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References
Range of evolution of shear stress with the shear rate for the
geopolymer and OPC formulation range.
Fig. 9
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