New Ways to Characterize and Control Thixotropy of Self Compacting

Concrete with the use of Dedicated Superplasticizers

Abstract: Self Compacting Concrete (SCC) has such outstanding flow

properties that it is now widespread in many countries, covering various
applications like heavy precast elements or large jobsite projects. However,
its ability to fill complex or long formworks is sometimes reduced, as
thickening processes can occur at rest or slow motion. Better know as
thixotropy, this behaviour, reflecting a change in the concrete microstructure
under very low shear rates, is described in the present study.

In order to understand and quantify the impact of different polycarboxylate

superplasticizers on thixotropy, various tests were performed, first on a
grout scale, by recording flow curves with a rheometer, then on a concrete
scale, whereas a newly designed box-flow test was conducted. It led us to
compare efficiently the formwork-filling ability of SCC designed with different
admixtures, confirming at the same time the trends observed with the
rheometer.

Out of this study, a superplasticizer was selected and tested successfully in

the field, confirming to be robust against thixotopy, as it would allow a faster
and more homogeneous formwork filling.

Since it was developed in Japan in the 1980’s, Self-Compacting Concrete

(SCC) has been successfully introduced in many countries around the world
during the last decade, due to its ability to cast without vibration heavily
reinforced elements or complex geometrical shapes, improving significantly
the final time of completion and reducing labour cost and noise. As a
consequence, the use of SCC has clearly gained importance in the Indian
concrete industry nowadays, especially in large jobsite projects.

However, concrete producers report sometimes a “wrong behaviour of SCC”

(in their own words), which reveals that high slump flow balanced with a
reasonable viscosity is not always the key of success. Typically, by casting
long shape elements, concrete may lack some “free flow”, i.e. the flow slows
down and finally stops too close from the casting point, making it necessary
to move this point along the formwork. Such practical industrial problems
show the growing importance of considering not only the classical rheological
parameters – yield stress and apparent viscosity – but also the slow
“structuration” of the cement paste that can occur at rest or at low shear
rate, better known as thixotropy.

It is well known that superplastizers drive a major part of SCC rheology.

Therefore, after analysing the thixotropy mechanisms and their
consequences on concrete properties, we will investigate how
superplasticizers can influence thixotropy, on two different scales: first a
grout scale modelling of flow, then a concrete validation scale, in lab and in
the field, with the use of specific tools that were designed especially for
measuring thixotropy – as the common tools such as Abrams slump cone, V-
funnel or even L-Box give rather limited information on this particular
property.
Thixotropy of SCC

Traditionally, rheology – defined as the science of flow – of high flowable

concrete and SCC uses two parameters to describe the flow in steady state:
these are yield stress and plastic viscosity, both related by a linear
relationship called Bingham model (Figure 1).

In the classical modelling where fresh concrete is considered as a

concentrated suspension of aggregates surrounded by cement paste, the
solid particles interact to build a three dimensional network that resist flow
at low shear stress. The yield stress is related to the minimal force required
to overcome this cohesion and initiate the flow. It is directly correlated in
concrete to the slump value. As far as viscosity is concerned, it corresponds
to the ratio of the shear stress to the shear rate, which is constant in this
case.

However, a closer look at casting operations in the field leads us to consider

some subtle variations of yield stress and viscosity in time, especially when
concrete is at rest or moving very slowly. As a typical example, many
concrete producers state that not every SCC is able to fill “freely” elongated
or complex formworks, observing that the flow rate slows down until it stops
before reaching the end of the formwork. This reflects the fact that the
rheology of SCC at low shear rate is in fact non linear and time dependant.
Such a situation highlights a so-called thixotropic behaviour. Precisely,
thixotropy can be defined as:
1) A continuous decrease of viscosity and yield stress with time, when a
shear force is applied to a sample that was previously at rest ;
2) The subsequent recovery of the initial state when this force is no more
applied.

This evolution of rheology in time can be explained by a breakdown of the

flocculation state of the cement particles, induced by shear. It is important
to note that such changes from a flowable fluid to a solid like elastic gel are
reversible phenomena. Although thixotropy was first called in the litterature
“’abnormal setting” [1], it has nothing to do with cement hydration
processes, which are irreversible. In case of a thixotropic concrete, an
efficient mixing can simply erase the consequences of a long resting time on
the flocculation state, whereas no mixing energy can reverse the setting
process.
While thixotropy is a property that does not affect the concrete flow
behaviour in steady state (activities like, mixing, continuous pumping, e.g.),
it is relevant on the other hand to take it into account during transient
phases, which are typically the pouring and casting steps, as previously
described. Depending on the application, thixotropy can actually show some
positive practical consequences: shape stability for example is often required
for shotcrete and slip form construction, so that concrete can respectively
adhere on the substrate or hold the shape right after casting and without
support from formwork. However, in case of SCC, thixotropy offers generally
more drawbacks than advantages. Certainly, this behaviour can help on the
one hand to avoid static segregation of coarse aggregates and decrease the
hydrostatic pressure on the formwork, but on the other hand the following
negative effects can be seen:
– a partial reduction of the “self-placing” ability of the concrete in case of
a slow casting and / or long size elements
– with lower water / cement ratios (as Indian practice is for high strength
concrete), thixotropy tends to increase ;
– in case a thixotropic concrete is poured in more than one layer, it will be
advised not to wait too long between each pouring, otherwise the interface
will be marked, which could affect not only the aesthetics but also the
mechanical properties
– thixotropy can increase bug holes on the surface of the finished element,
as the concrete thickens before air bubbles have time to get out
– as far as pumped concrete is concerned, after pumping stops, thixotropy
can sometimes get strong enough to block the pump while restarting it

Thixotropy Evaluation on a Grout Scale

The growing awareness of the role of thixotropy in SCC led us to investigate

the effect of polycarboxylate superplasticizers on such phenomena.
Superplasticizers, as we know, interact on the one hand with cement
particles, providing dispersion that is so critical for achieving the typical flow
of an SCC. On the other hand, thixotropy being related to interactions in
between cement particles, the careful choice of the superplasticizer molecule
may help to control it. In order to check this assumption, our first
rheological approach was based on a “concrete –equivalent grout”, a
methodology developed by N. Roussel [2], [3] in which the rheological
characteristics, measured by a rheometer, are mostly driven by the cement
paste Therefore, an arbitrary size limit of 0,315 mm was selected to fit the
rheometer gap, and all materials were combined into a grout simulating the
concrete grading curve at 0,315 mm maximum particle size (Figure 2).

Test Protocol

Three different PCP based superplastizers SP1, SP2 and SP3 were tested for
the purpose of our study, SP1 being a common superplasticizer, SP2 and
SP3 being two products specifically designed for thixotropy reduction.

For each admixture tested, water and admixture were weighted in a Krups
YY8506FD mixer bowl. The dry powders (Figure 3) were added during the
first 30 seconds of mixing at speed 1 with a leaf-shaped blade. The mixing
speed was then increased to speed 7 for 1 minute, then stopped for 30
seconds (to scrape the sides of the bowl) before applying a last speed 7 –
mixing stage. The dosage of each superplasticizer was adjusted in order to
work at an equal mini-slump flow of 105 + 5 mm, a value determined from
the slump flow of a reference concrete.

The sample was loaded on the lower plate of a Kinexus rheometer (Malvern
Instruments, U.K.) equipped with a serrated parallel plate geometry (1 mm
gap). The procedure, in two steps for evaluating the influence of thixotropy
both on shear stress and viscosity, started five minutes after the beginning
of mixing with a one minute pre-shear at 200 s-1, as represented in Figure
4

1) A logarithmic shear rate decrease by steps from 200 down to 0.01 s-1
(each stress data point was sampled at the steady state whenever possible
in order to build the flow curve)
2) A re-shearing followed by a 4 Pa constant rotation, in order to
simulate a gravel sedimentation

Results
Figure 5 displays the evolution of the shear stress as a function of the shear
rate for the three grouts. As expected, the flow curves at high values of
shear rate follow a linear trend, which fits the Bingham model. The flow is
well steady in this area. But below a critical shear rate – modelling a
situation where concrete flows very slowly – the rheological behaviour
changes significantly, since the shear stress increases when lowering the
speed. In this area the flow is not steady anymore. The corresponding
minimum value for shear stress stands as the point for which the tendency
of the grout to rebuild overcomes the applied shear, thus highlighting a
thixotropic behaviour.

Some differences between superplasticizers can also be observed, revealing

different ways of action. Whereas SP1 shows high stress values at low
speed, with a clear growing tendency, SP2 and SP3 have much lower
minimum shear stress values, associated with rather flat curves. Their
minimum shear stress values look also shifted towards lower shear rates,
which indicates a better ability to maintain a steady flow behaviour in such
conditions. Altogether it shows that these two superplasticizers have a
reduced impact on the structure build-up, therefore on thixotropy, their
action being essentially limited to reduce the yield stress.

Figure 6 displays the evolution of the viscosity as a function of time (30 min
sequences) when a constant stress of 4 Pa is applied, simulating the force of
a coarse aggregate sedimentation. All curves display some changes of
viscosity in time, a clear sign for thixotropy phenomena. But different
behaviours between the superplasticizers can be seen once again: the
viscosity with SP1 grows very fast within the first 10 minutes, leading to a
near gelification of the paste, whereas SP2 and SP3 show only a light
increase of the viscosity, certainly useful against static segregation, but
more importantly affecting not too much the rheology of the paste.
Thixotropy Evaluation on a Concrete Scale

Laboratory Test Protocol

The rheological analysis on grout led us to conduct concrete scale trials in

order to validate the previous trends. A experimental tool was needed to
evaluate concrete thixotropy. It appears in fact that values obtained with
common laboratory devices like Abrams slump cone, V-funnel flow time, J-
ring flow or even L-Box generally depend on several rheological properties
simultaneously, such as yield stress, viscosity and thixotropy, making it
quite difficult to access the intrinsic characteristic of thixotropy. The need for
its precise determination promoted the development of a specific equipment,
nicknamed CHRYSOBox (Figure 7). This box, robust and easy to handle in
laboratory scale as well as in the field, is basically made of a rectangular
container separated in two parts of equal size by a removable gate. The two
compartments on the left side are filled simultaneously with concrete right
after the end of mixing and the inner wall is then lifted 2, 6 or 10 minutes
later. The time taken by the concrete to reach the opposite end of the box is
measured at each resting time and gives a practical evaluation of structure
build-up during the considered time interval.
The concrete tested in the study was a typical SCC for pre-stressed
applications, following the European standards (Figure 8). In a laboratory
SKAKO horizontal mixer, sand and gravel were blended and pre-wetted for 5
minutes with a part of the batching water. The binders were then added in
dry state. The admixtures were dosed with the remaining water, subtracting
their water content from the total amount of liquid, and then incorporating
the aqueous part with the rest of the blend into the mixer for 3 minutes and
30 seconds.

Results
Three SCC batches were prepared with the superplasticizers studied
previously at grout scale. The dosages were adjusted in order to achieve a
700-720 mm slump flow with the Abrams cone. The CHRYSOBox filling times
are displayed in Figure 9. For a 2 minute resting time, all three products are
comparable. For a 6 minute resting time, SP1 seems less efficient in slowing
down structure build-up. For a 10 minute resting time, SP3 shows a
significantly faster filling after wall lifting, which confirms to be the best
admixture for limiting thixotropic effects.

Compressive strengths were checked on 15x15x15 cm³ cubes cured at 10°C

for 16h or 20°C for 24h. Figure 10 shows that the flow improvement brought
by SP3 does not induce a decrease in strength, even in the low temperature
scenario. In the same conditions, SP2 induces a strength decrease due to
both its slightly higher dosage and its polymer architecture.

Industrial Tests

SP3 was tested on an industrial scale versus the current superplasticizer of

the factory in a typical pre-stressed beam application. Results are shown in
Figure 11.

For the same target slump flow of 680 mm, the required SP3 dosage was
1% by weight of total binder versus 1.25% for the current superplasticizer.
Despite the lower dosage, faster form filling was obtained, as observed by
the customer. Moreover the decrease in dosage led to lower risks of
segregation and allowed even a 6 MPa gain at 14h, thus an earlier stress
release and a faster manufacturing cycle. Surface finishing was noticeably
improved as well as the final facing quality (no bug holes).
CONCLUSION

The testing program which was conducted, first on a grout scale, then on a
concrete scale, aimed for a characterization and quantification of thixotropy,
a phenomenon not always easy to measure on concrete with the classical
methods such as slump flow or V-funnel tests. Therefore a new specifically
designed tool named CHRYSOBox, usable on a lab scale as well as in the
field, was developed for a more precise assessment of formwork-filling
ability after rest and at low shear rates.

This work highlighted the important role of the admixture chemistry on

structure build-up and break-up under shear. It led us to select specific
polycarboxylate superplasticizers able to reduce partly the thixotropic
behaviour, like the SP3 mentioned in this study. This product, launched later
on as CHRYSO® Fluid Premia 500, inaugurated a new range of admixture
solutions called Fill-Free® Technology, optimizing the capability of SCC to
achieve homogeneous, uniform and “free” casting with thixotropy under
control.

References

– G.L. Kalousek,“A new instrument for measuring thixotropy”, Cement

and Concrete Research, 3 5(1973), pp 315-323.
– N. Roussel, “Thixotropy modelling at local and macroscopic scales,”
Journal of Non-Newtonian Fluid Mechanics, vol. 117, no. 2–3, pp. 85–95,
Feb. 2004.
– L. Ferrari, P. Boustingorry, A. Pineaud, L. Bonafous, “From cement grout
to concrete scale: a study of superplasticizer-desig-controlled thixotropy to
match SCC application requirements”, Proceedings of the 7th RILEM
International Conference on Self-Compacting Concrete and of the 1st RILEM
International Conference on Rheology and Processing of Construction
Materials, pp 285-292.