EFFECTS OF NANOSILICA ADDITIONS ON CEMENT PASTES

A Porro J S Dolado I Campillo

E Erkizia Y de Miguel Y Saez de Ibarra
NANOC-LABEIN
A Ayuela
Donostia International Physics Centre
Spain

ABSTRACT. Some interesting experimental results derived from the addition of nanosilica
particles into cement pastes are reported. The addition of nanosilica to cement pastes has
been carried out, either in powder form or as a colloidal suspension (stabilised by a
dispersant), and has been compared to the addition of microsilica. It has been found that
nanosilica additions improve the mechanical properties (compressive strength) of the
resulting cement paste with respect to additions of microsilica. Furthermore, it has been seen
that this effect cannot stem from a pozzolanic reaction. In fact, XR-Diffraction studies have
confirmed that, contrary to the case of microsilica or silica fume, in the case of nanosilica, the
consumption of Ca(OH)2 is completely negligible. Consequently, the improvement of the
mechanical properties must be attributed to a new and yet unidentified process. Some 9Si
NMR experiments have been carried out, as it is expected that this NMR study could lead to
an understanding of this intriguing result. It is noteworthy that these experiments suggest that
nanosilica promotes the growth of Si chains, and thereby the formation of denser structures.

Keywords: Cement paste, Pozzolanic reaction, Nanosilica, Chain growth.

Dr A Porro is the head of the NANOC-LABEIN group. His research interests cover different
topics, such as composites, smart materials or metamaterials. In general, his research pursues
the employment of Nanotechnology as a competitive tool for the Construction Sector.

Drs J S Dolado, I Campillo, E Erkizia and Y de Miguel work at NANOC-LABEIN, where

their research focuses on the development of high-performance materials. Although their
interests cover different sorts of materials, they are mainly focused on the study of
cementitious materials, and the study of the growth of silicate chains is one of their main
priorities.

Ms Y Saez de Ibarra obtained her degree in Physics in 2001. She is currently doing her
PhD studies under the supervision of Dr. I. Campillo. Her thesis is devoted to the
characterisation of different technological matrices by means of scanning microscopy.

Dr A Ayuela works at the Donostia International Physics Centre, and his research is
currently devoted to provide, by means of ab-initio calculations, a theoretical framework for
different aspects with regards to Nanotechnology.

Downloaded by [ University of Ottawa Library System] on [14/09/16]. Copyright © ICE Publishing, all rights reserved.
 88 Porroetal

INTRODUCTION

Cement based materials are very complex materials. Even their simplest form, the cement
paste, is still a poorly understood system. In basic terms, it can be said that a cement paste is
a porous system composed of Portlandite crystals (Ca(OH)2), and a Calcium Silicate Hydrate
product known as C-S-H gel [1,2]. Cement pastes are quasi-brittle materials and their
mechanical properties basically depend on the porosity and the gel/space ratio [3,4]. This is
the reason why it is interesting to achieve cement pastes with large amounts of C-S-H gel.

Doubtlessly, the addition of silica fume (SF) (also known as microsilica or condensed silica)
is the most common route to achieve an increase in C-S-H formation, and many studies have
focused on this [5,6,7,8]. Basically the interest of SF is based on the fact that the silica fume
reacts with the Portandite and forms more CSH gel, i.e. following the so-called pozzolanic
reaction [1,2]. As a consequence of this reaction, both a general refinement of the porosity
and a larger amount of C-S-H gel are achieved.

However, and paradoxically, the effect of adding nano-silica has not been thoroughly studied.
As far as we know, few studies have been reported on this issue, and have mainly
concentrated on rheological and workability aspects [9,10,11,12]. To the best of our
knowledge there has been no systematic study on the mechanical properties and on their
relation to the C-S-H modification. Only recently some studies have been published in this
direction [13,14,15]. The work presented hereafter will (i) provide more experimental
evidence that confirms that the addition of nanosilica improves the mechanical properties,
and (ii) it will reveal that the colloidal silica promotes the growth of the C-S-H chains by
means of a new and yet unidentified mechanism that does not lead to
portlandite consumption.

EXPERIMENTAL SET UP

In this section, only the most remarkable procedures will be described, since a detailed
explanation of the experimental set-up can be found elsewhere [15]. The pastes employed in
this work were made from CEM I 52.5 R. This type of cement has been selected because it
presents the finest granulometry of all commercial cements, which is best suited for the
inclusion of nanomaterials.

Different kinds of samples have been prepared. Besides plain Portland cement pastes (PC)
with no addition, others with microsilica or silica fume (SF) have been made, to compare
with the cases of nanosilica additions. Furthermore, different forms of nanosilica have been
taken into account, i.e., agglomerated silica forms (ADS), and colloidal forms (CS) stabilised
by dispersants. The main features of the employed nanosilicas are summarised in Table 1.

After mixing, the cement pastes were cast into prism-shaped moulds (1x1x6 cm) and
compacted by vibration. The specimens were demoulded after 1 day at 90% relative
humidity, and stored at constant temperature (21°C) for 28 days. The cement and water
quantities were fixed to 100 g and 33 g respectively. Dry admixtures were added to cement
grains, while the colloidal silica samples were directly added to the mixing water.

Downloaded by [ University of Ottawa Library System] on [14/09/16]. Copyright © ICE Publishing, all rights reserved.
 Nanosilica in Cement Pastes 89

Table 1 Characteristics of the employed micro and nano-silica

AVERAGE AVERAGE
NOTATION SUPPLIER SIZE SIZE PRESENTATION
(PARTICLE) (GRAIN)
Silica
SF SIKA 0.1 um 0.1 um Black powder
Fume
NYACOL
Nano
Nyasil 20 ADS 20 Technologies
20 nm 1.44 um White powder
Inc.
NYACOL
Nano
Nyasil 5 ADS 5 Technologies
5nm 2,50 j^m White powder
Inc.
NYACOL Colloidal silica
Nano stabilized in Ethylen
DP 5820 CS 20EG 20 nm 20 nm
Technologies Glycol
Inc. % SiO2 = 30 %
Colloidal silica
Levasil stabilized in aqueous
CS30 BAYER 30 nm 30 nm solution by Na2O.
100 % SiO2 = 45 %
%Na 2 O = 0.15%
Colloidal silica
stabilized in aqueous
Levasil
CS 15 BAYER 15 nm 15 nm solution by ammonia.
VPAC %SiO2=15%
% ammonia= 0.1 %

RESULTS
The effect of the additions of the different nanosilicas on the compressive strengths (at
28 days) of the different cement pastes are shown in Figure 1. It can be seen that the addition
of silica fume (SF) (represented by white diamonds) tends to lower the strength of the paste,
while all varieties of nanosilica clearly increase the compressive strength at different rates
depending on the specific nanosilica type.
The behaviour of the silica fume is mainly due to i) the absence of any superplasticizer in the
mix, which prevents microsilica from developing its effect, and ii) the low level of addition
that has been employed. Typically the silica fume needs to be present in well over 8-10 % in
weight of cement to be efficient, whereas in this study the selected range has been between
2% and 12%. In any case, for the highest percentages an increase can be observed.
On the other hand, the addition of the two types of agglomerated silica, ADS-20 (represented
by solid circles) and ADS-5 (open circles) involve a steady increase of the compressive
strength as a function of the amount of addition. The former consists of grains of
agglomerated silica with primary particle sizes of 20nm and the latter of 5 nm. This can
explain the results in Figure 1, in which ADS-5 shows a slope four times larger than that of
ADS-20, since as a simple rule of thumb, one could suppose that the smaller the particle the
larger its reactivity, and the more C-S-H gel produced by pozzolanic reactions. However, as
it will be shown in the section devoted to the XR Diffraction studies, this kind of arguments
must be carefully employed, as the involved phenomena are much more complex
than expected.

Downloaded by [ University of Ottawa Library System] on [14/09/16]. Copyright © ICE Publishing, all rights reserved.
 90 Porroetal

In the case of colloidal silica, the improvement is even more pronounced. The CS 30 (open
triangles), which is stabilised by a solution of Na2O in water, shows a remarkable increase
with respect to ACS-20 and a slight increase with respect to ADS-5. This can be again
understood by taking into account that in this case the nanosilica is purely nano, i. e., it is not
agglomerated. As expected, the most dramatic changes are shown by the smallest colloidal
silicas, the CS-15 (solid triangles) and CS-20-EG (white squares). In the former, the
nanosilica is stabilised by ammonia, the particle diameter is 15 nm and the concentration 30
%, whereas the latter is stabilised by ethylene glycol, its particle diameter is 20 nm, and the
concentration 30%. It is noteworthy that these large improvements in the compressive
strength are possible even at very low amounts of addition. It is also remarkable that in the
case of CS-20-EG, there is a point at which the compressive strength begins to decrease
quickly. This abnormal behaviour is clearly brought about by the dispersant utilised
(ethylene glycol), since it has been found that small amounts of ethylene glycol reduce
drastically the strength of cement pastes.

4 6
gr. of admixture
% ADDITION, by cement

Figure 1 Effect of the addition of nanosilica on the compressive strength of cement pastes

It is obvious that the microstructure of the formed hydrated species must be somehow
modified by the addition of the nanosilica. Furthermore, and as commented before, the
mechanical improvements obtained through the addition of silica based elements is generally
addressed as coming from pozzolanic reactions under which the silica reacts with the
Portlandite to form CSH gel.

To verify the existence of such reactions, different XR-Diffraction measurements have been
carried out (at 28 days). By means of this spectroscopic technique, pozzolanic reactions can
be easily monitored by observing the consumption of Portlandite. The equipment that has
been employed in this study is a X'PERT PRO. Attention has been paid to the Portlandite's
peaks of 2 Theta -18° and 2 Theta -34°.

Downloaded by [ University of Ottawa Library System] on [14/09/16]. Copyright © ICE Publishing, all rights reserved.
 Nanosilica in Cement Pastes 91

SlicaFlnB
200-

100-
og
U- j \^&
100-
2g j I
Wv
o- i)
150-
6g
100- j ^ Jl..
50-
0: j L \
100-
50-
o-l
k- tiL+A
10 20 30 40 50 60 70
Position [°2Thela]

Figure2 XRD patterns for different quantities of SF

As can be seen in Figure 2, the Portlandite consumption increases by increasing the

percentage of silica fume. For instance, an addition of 12 g of SF means nearly a 50%
reduction (from -100 counts to ~ 50 counts) in the intensity of the peak 2 Theta -18°. This
result was nevertheless expected, as it is well known that silica fume takes part in pozzolanic
reactions. The same behaviour has also been found for the ACS 20 and ACS 5. The XR
diffraction pattern of the latter is shown in Figure 3. Thus, and in view of these results, the
agglomerated nanosilica also seems to follow pozzolanic reactions. Moreover, it is
interesting to point out that the consumption of Portlandite is larger in the case of the
agglomerated nanosilica than in the case of silica fume, and to note that the peak 2 Theta
-34° is also largely diminished in the case of agglomerated nanosilica.

However, and contrary to the previous cases, colloidal nanosilica does not involve Ca(OH)2
consumption, as can be seen in Figure 4. This behaviour is clearly intriguing, and therefore
raises the question of which is the underlying mechanism that leads to the observed
mechanical improvement.

ADS-5
200-
Ogr
100-

0"
150-
100- 2gr
50 •
0 : >TSl1 mi Him
rt^W^lM
100 - 6gr
o 50-
0-
100-

50-
12 gr
inj0T*y
o-
10 20 30 40 50 60 70
POSITION [°2Theta]

Figure 3 XRD pattern for different quantities of ADS-5

Downloaded by [ University of Ottawa Library System] on [14/09/16]. Copyright © ICE Publishing, all rights reserved.
 92 Porroetal

CS-15
2UU- :::.::;:::;::q;.:.:-™"»: ""* •----j"—"

100-
Ogr
• r
150-
i
0,26 gr 1 ^
«>n-
o-
150-
0,78 gr
•4 H i
100-
50- OKsssd
15 U oj j :.. •*• i •
100*
1.3 ST ,
50-
n- ft! IrF
H-TT,

10 20 30 40 50 60 70
POSITION [°2TTieta]

Figure 4 XRD spectra for different quantities of CD-15

Nevertheless, this unexpected experimental evidence suggests that the C-S-H gel must be,
somehow, modified by means of a new and unaddressed mechanism. For this reason, and to
shed more light on these puzzling results, different 29Si NMR experiments have been carried
out (using a Bruker DXR 300 spectrometer with CPMAS probe). This technique is a very
suitable tool to study the polymerisation of the C-S-H gel [2,16,17]. In the case of C-S-H,
and in general in silicates, a Qn nomenclature is used for the peaks, where Q n is the chemical
shift of a silicon atom which is bound to n bridging oxygens. In Figure 5 the obtained 29,Si
NMR spectra are plotted for the particular case of colloidal silica (CS-30 and CS-15).

-62 -64 -66 -68 -70 -72 -74 -76 -78 -80 -82 -84 -86 -88 -90 -92 -94 -96 -98

(ppm)
29
Figure 5 Si NMR spectra for cement pastes at 28 days, obtained by means of adding 1.8%
(in weight of cement) of CS-30 and CS-15.

Downloaded by [ University of Ottawa Library System] on [14/09/16]. Copyright © ICE Publishing, all rights reserved.
 Nanosilica in Cement Pastes 93

The first thing that we would like to remark in view of Figure 5 is that only QO, Ql and Q2
peaks appear. This is important since the inexistence of Q3 peaks and Q4 peaks confirms
that colloidal silica has reacted somehow. Although not shown in Figure 5, a similar trend
has been observed for the other cases (SF, AS). Therefore, and to best quantify the effect of
each addition, the obtained main chain lengths (MCL) are represented in Figure 6. These
MCLs are dimensionless quantities that stand for the number silicon atoms per chain, and
they are directly calculated from the known formula MCL= 2(Q1+Q2)/Q1 [17].

In the view of these results it can be seen that i) both the addition of silica fume and the case
with agglomerated nanosilica lead to a slight increase in chain length when compared to no
addition, going from 2.47 to -2.77, (ii) the colloidal silica CS-30 and CS-15 promote a much
larger increase, with a mean chain length of 3.3 and 3.5 respectively. Thus, keeping in mind
that the experimentally observed lengths obey the rule m=3n-l for n=l, 2 [1] in the case of
addition of the colloidal silica, the formed C-S-H presents an equally weighted distribution of
dimers and pentamers, even at 28 days.

Consequently, these results provide clear evidence for the large impact of the colloidal
nanosilica on the modification of the C-S-H gel and a possible explanation for its mechanical
improvement. In fact, a clear correlation between the chain length and the mechanical
properties of gel C-S-H has been recently observed by means of nanoindentation experiments
[18].

3.5
<1GTH

a 2.5

• II
<
_i_
o
2

1.5
III
III
1

0.5
III
III
0
PORTLAND ADS-20 ADS-5 CS-15 CS-20-EG
CEMENT

Figure 6 Main chain lengths of the CSH chains at 28 days, for the employed additions at
1.8% in weight of cement

Downloaded by [ University of Ottawa Library System] on [14/09/16]. Copyright © ICE Publishing, all rights reserved.
 94 Porro et al

CONCLUSIONS

In conclusion, we have analysed the effect of the addition of different types of nanosilica to
Portland cement paste. We have seen that the addition of nanosilica raises the compressive
strength of cement paste at 28 days. The increase of the compressive strength due to
colloidal silica is higher than that for agglomerated silica. Furthermore, when the same type
of nanosilica but with different particle sizes are compared, the results show that the
nanosilica with the smallest particle size gives a better improvement of the compressive
strength. The only exception is the CS 20 EG nanosilica. The addition of this product to
cement gives lower compressive strength once a certain amount of addition is passed. But
this is due to the presence of ethylene glycol, the stabilising agent, as it is well known that
organic compounds are detrimental to cement and its properties.

The X-ray diffraction spectra have shown that when silica fume or ADS (agglomerated dry
silica) is added, there is consumption of Ca(OH)2 (Portlandite) with time, so they follow
pozzolanic reactions. However when CS is added to the cement, no reduction of the Ca(OH)2
peaks is observed in the XRD spectra.

Finally, the data obtained by NMR indicate that longer silicate chains are obtained in the C-S-
H gel when adding CS than when adding any other type of silica. This result confirms the
large impact of the CS addition on C-S-H chains, and reveals a new growth mechanism,
maybe based on the reaction of CS with the already formed C-S-H.

We suggest that this experimental evidence opens a new path in the way of achieving High
Performance Concretes, (HPC) that hopefully does not compete with traditional procedures
based on microsilica additions. Thus, the future of CS seems highly promising. Obviously,
much more work must be done on it, since many questions, such as the way in which the
colloidal nanosilica might enter the C-S-H gel, remain unsolved.

In this respect, a multidisciplinary approach, including both experiments and computational

models is required. In fact, an ongoing theoretical study has enabled to predict and partially
understand many of the processes that take part in the C-S-H silicate chain growth [19].

ACKNOWLEDGEMENTS

The authors wish to acknowledge the Bayer Corporation for providing free samples of
Levasil and Cementos Lemona and Cementos Rezola for providing the CEM 52.5 R.
Moreover we wish to acknowledge The Basque Government for the concession of the project
NANOMAT, (ETORTEK programme), since this research has been done under its
framework. Finally, we also extend our acknowledgments to the anonymous reviewers for
their enriching comments.

REFERENCES

1. TAYLOR H.F. Cement Chemistry. Academic Press, New York, 2003.

2. BERSEN J. and BARNES P. Structure and Performance of Cements. Spon Press, 2002.

Downloaded by [ University of Ottawa Library System] on [14/09/16]. Copyright © ICE Publishing, all rights reserved.
 Nanosilica in Cement Pastes 95

3. MINDESS S. andYOUNG J.F. Concrete. Prentice-Hall, Inc. Englewood Cliffs, NJ.

07632,(1981).

4. POWERS T.C. and BROWNYARD T.L. Studies of the Physical Properties of

Hardened Portland Cement paste. Journal of the American Concrete Institute, vol 18,
No. 2 pp 101-131 (1946)

5. FIDJESTO P. and LEWIS R. Microsilica as an addition.Chapter 12 in Lea's Chemistry

of Cement and Concrete. Arnold Publishers, London (ISBN 0 340 56589 6), (1998).

6. HELL AND S. et al Condensed silica fume in concrete.FIP State of the Art Report,
Thomas Teldford, London, (ISBN 0 72722 1373 6), 37 pp, (1988)

7. MALHOTRA V.M. et al. Role of the silica fume in concrete: a review. Adv. Concr.
Technol. (1992).

8. SELLEVOD E.J. et al. Selected properties of high performance concrete. "Proc, Engg.
Foundation Conf."(1994)

9. CHANDRA S. and BERGQVIST H. Interaction of silica colloid with portland cement,

Proc. Int. Congr. Chem. Cem. Vol. 3 (1997), 3iil06, 6pp.

10. J. BASTIEN et al.. Cement grout containing precipitated silica and superplasticizers for
post-tensioning, ACI Materials Journal 94 (1997), 291

11. BJORDAL A. et al. Colloidal silica cement: description and use in North Sea
operations, Proceedings of Offshore Europe 93 published by the Society of Petroleum
Engineers (1993), 431

12. GREENWOOD P. et al. Patent Number WO 200190024 Al.

13. COLLEPARDI M. et al. Influence of Amorphous Colloidal Silica on the Properties of

Self-Compacting Concretes . Proceedings of the International Conference "Challenges
in Concrete Construction - Innovations and Developments in Concrete Materials and
Construction", Dundee, Scotland, UK, 9-11 September 2002, pp. 473 - 483.

14. COLLEPARDI M. et al. Recent Developments of Special SCC's, Proceedings of

Seventh CANMET/ACI International Conference on Recent Advances in Concrete
Technology, Las Vegas, USA, 26-29 May, pp. 1-18, (2004)

15. CAMPILLO I. et al. High-performance nanostructured materials for Construction. 1st

International Symposium on Nanotechnology in Construction. Paisley (2003).

16. RAMACHANDRAN V.S. and BEAUDOIN J. Handbook of Analytical Techniques in

Concrete Science and Technology. Building Materials Series.(2001)

17. BROUGH A.R. et al. In situ solid-state NMR studies of Ca3Si05: hydration at room
temperatures using 29Si enrichment. Journal of Materials Science 29 (1994) 3926-3940

Downloaded by [ University of Ottawa Library System] on [14/09/16]. Copyright © ICE Publishing, all rights reserved.
 96 Porroetal

18. CONSTANTINIDES G. and ULM F.-J. The effect of two types of C-S-F on the
elasticity of cement-based materials: Results from nanoindentation and micromechanical
modelling. Cem. Concr. Res. 34 (2004)

19. AYUELA A. et al. On the silicate chains growth in cements by adding colloidal silica,
To be published.

Downloaded by [ University of Ottawa Library System] on [14/09/16]. Copyright © ICE Publishing, all rights reserved.