Construction and Building Materials 35 (2012) 666–675

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Construction and Building Materials

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Effects of nanosilica addition on workability and compressive strength of

Portland cement pastes
M. Berra a,⇑, F. Carassiti b, T. Mangialardi c, A.E. Paolini c, M. Sebastiani b
a
Ricerca sul Sistema Energetico – RSE S.p.A., Via Rubattino 54, 20134 Milan, Italy
b
Department of Mechanical and Industrial Engineering, University of Rome ‘‘Roma Tre’’, Via della Vasca Navale 79, 00146 Rome, Italy
c
Department of Chemical Engineering, Materials and Environment, University of Rome ‘‘La Sapienza’’, Via Eudossiana 18, 00184 Rome, Italy

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

Article history: The effect of nano-size particles of amorphous silica (nanosilica) on the rheological behaviour and
Received 16 December 2011 mechanical strength development of cementitious mixes is addressed. Mini-slump and rheometric tests
Received in revised form 15 March 2012 were carried out on cement pastes made with three dose levels of nanosilica at different water/binder
Accepted 25 April 2012
ratios. Cement paste workability resulted to be significantly lower than expected for the adopted
Available online 31 May 2012
water/binder ratios, as a consequence of instantaneous interactions between nanosilica sol and the liquid
phase of cement pastes, which evidenced the formation of gels characterised by a significant water reten-
Keywords:
tion capacity. The resulting reduction of the mix workability was avoided by suitable addition procedures
Nanosilica
Cement
of superplasticizers. No appreciable improvement in the compressive strength development of cementi-
Workability tious mixes by nanosilica addition was observed, in contrast with some results from literature. This con-
Gel formation firms conflicting experience on the problem, but some parameters affecting the strength development
Hydration were identified and discussed.
Compressive strength Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction synthetically in the form of slurry of ultra-fine particles of amor-

The use of active mineral admixtures (supplementary cement-
ing materials, SCM) such as condensed silica fume, coal fly ash, nat-
ural pozzolan, or ground granulated blast furnace slag in concrete
mix formulations is an effective way of reducing the Portland ce-
ment clinker consumption and then reducing the related CO2 emis-
sions. It also represents an effective way of improving the
durability of concrete structures [1,2], even if a decrease of carbon-
ation resistance has been ascertained [3,4], in case of reinforced
concrete.
Thus, the use of supplementary cementing materials have be-
come an integral part of Portland cement concrete production,
and the research on ‘‘new’’ materials with supplementary cement-
ing potential, including waste or recycled materials (for example,
fine glass powder), is receiving considerable attention from the sci-
entific community.
Recently nanotechnology is being used or considered for use in
many applications and it has received increasing attention also in
building materials, with potential advantages and drawbacks being
underlined [5,6]. In this field, a new pozzolanic material, produced
⇑ Corresponding author. Tel.: +39 02 39925920; fax: +39 02 39924608.
E-mail addresses: mario.berra@rse-web.it (M. Berra), f.carassiti@stm.uniroma3.
it (F. Carassiti), teresa.mangialardi@ingchim.ing.uniroma1.it (T. Mangialardi),
paolini@ingchim.ing.uniroma1.it (A.E. Paolini), m.sebastiani@stm.uniroma3.it
(M. Sebastiani).
phous silica, also called ‘‘nanosilica’’ (NS), was introduced into
the market. Due to the nano-scale size of particles, nanosilica
potentially could be more effective than condensed silica fume,
the latter being acknowledged as one of the most valuable tradi-
tional SCM for improving concrete durability.
At present, a significant number of works dealing with the use
of nanosilica in cement-based materials is available in the litera-
ture [7–30]. However, there is a limited knowledge about the
mechanisms by which nanosilica affects the flow properties of
cementitious mixes. Furthermore, the literature data appear to be
contradictory about the influence of nanosilica on the mechanical
strength development of such materials.
With regard to the effect of nanosilica on the rheological behav-
iour of cementitious mixes, rheometric studies on cement mortars
incorporating superplasticizer [17] or not incorporating superp-
lasticizer [25] agree in indicating that the addition of nanosilica
greatly increases the water demand of cementitious mixes, as com-
pared to control ones. This effect is related primarily to the consid-
erable increase of the yield stress and, to a minor extent, to the
increase in plastic viscosity. However, no pertinent experiment
was presented to explain the mechanism by which nanosilica pro-
duces a considerable increase in the yield stress during the early
phase of mixing. The only hypothesis is that the presence of nano-
silica decreases the amount of lubricating water available within
the interparticle voids, as a consequence of a denser solid particle
packing produced by silica nanoparticles [25].

0950-0618/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2012.04.132
 M. Berra et al. / Construction and Building Materials 35 (2012) 666–675 667

With regard to the influence of nanosilica on the mechanical Table 1

strength development of cementitious materials, the addition of Physico-chemical characteristics and mineralogical compo-
sition of Portland cement (CEM I 32.5 N).
nanosilica to Ordinary Portland Cement (OPC) pastes was found
to increase the compressive strength to an extent that was depen- Oxide component (%)
dent on the NS content, water-to-binder weight ratio (w/b), and CaO 62.31
curing time [11,13,20,21,28]. Some researchers [11,20,21] also re- Free CaO 0.67
ported a progressive increase of compressive strength with increas- SiO2 21.23
Al2O3 4.44
ing nanosilica content over the range of NS dosages from 0.2 to 10– Fe2O3 1.90
12 wt.% of cement. With respect to pastes not containing NS (con- SO3 3.29
trol mixes), percentage strength gains up to 65% could be achieved Na2O 0.44
[20]. In contrast, Shih et al. [13] found a maximum strength gain K2O 0.83
Na2Oeq 0.99
(43%) for OPC pastes with 0.6 wt.%NS. The strength gain reduced
MgO 3.77
to 19% as the NS content was increased from 0.6 to 0.8 wt.%. SrO 0.12
In the case of Belite cement pastes [19], the addition of nanosil- Mn2O3 0.05
ica was found to reduce the compressive strength development (by P2O5 0.07
about 20%) up to curing times of 90 days. Only at 180 days, this TiO2 0.20
Loss on ignition 1.30
behaviour was completely reversed and the usage of nanosilica en-
Density (g/cm3) 3.15
tailed mechanical gain by about 12%. Blaine specific surface area (m2/kg) 270
Differently from what was reported for cement pastes, no Bogue potential constituent (%)
improvement in compressive strength was observed by Leemann C3S 47.69
C2S 24.89
and Winnefeld [17] for OPC concrete mixes (w/b = 0.50) containing
C3A 8.56
nanosilica and superplasticizer at dose levels of 1.5% and 0.5% by C4AF 5.78
mass of cement, respectively (curing times up to 28 days). How-
ever, recent studies by Givi et al. [29] and Nazari and Rihai [30]
have shown mechanical strength improvements for concretes
added with nanosilica. Table 2
The main objectives of the present study were: (i) to elucidate Physical and chemical characteristics of nanosilica
the mechanisms by which silica nanoparticles affect the flow prop- slurry.

erties and the rheological behaviour of cementitious mixes, (ii) to pH 10.2

develop an effective mixing procedure to counteract the adverse Silica content (wt.%) 30
effect of nanosilica on workability of Portland cement pastes and Titrable alkalis (wt.% as Na2O) 0.56
Density (g/cm3) 1.22
(iii) to verify the influence of nanosilica addition on the mechanical Viscosity (mPa s) 5.5
strength development of pastes processed by the mixing procedure Mean particle size (nm) 10
developed in order to accomplish adequate workability. Specific surface area (m2/g) 345
To achieve such goals, mini-slump and rheometric tests were
carried out to assess workability as a function of the NS content.
Stability tests on slurries containing different concentrations of admixture was commercialised as a superplasticizer with property of accelerating
nanosilica were also carried out to verify the water demand. Finally, cement hardening. The superplasticizer was added to cementitious mix after nano-
the mechanical properties of cement pastes as a function of the NS silica and OPC addition to mixing water (delayed superplasticizer addition).
content were analysed by compression tests (Rc, UNI-EN 196–1).

2. Materials and methods 2.1.1. Flow and rheological tests

2.1. Preparation and characterisation of fresh cement pastes
An ordinary Portland cement, CEM I 32.5 N according to European Standard
197–1, and a commercial slurry of silica nanoparticles containing sodium hydroxide
as a stabilizing agent (LUDOX SM30, Grace GmbH – Germany) were used for the
preparation of cement pastes. Table 1 gives the physico-chemical characteristics
and mineralogical compositions of Portland cement, also referred to as OPC. Table
2 gives the chemical and physical characteristics of the nanosilica slurry, along with
the mean size and the specific surface area of silica nanoparticles, as determined in
the present study. The specific surface area was measured by the BET method on
dry and degassed NS samples obtained from the as–received nanosilica slurry.
Dry NS samples were also analysed for chemical composition by traditional gravi-
metric and volumetric test procedures. The morphology and elemental composition
of silica nanoparticles were evaluated by Transmission Electron Microscopy (TEM –
FEI CM120 equipped with LaB6, double tilt, nanoprobe, analytical set-up) coupled
with Energy Dispersive Spectrometry (EDS – EDAX DX4i). Samples were prepared
by direct immersion of the TEM sample holder grid (formvar film on 3 mm copper
grid) in the NS slurry, followed by drying in air inside a clean box.
Three different dose levels of silica nanoparticles were selected for the prepara-
tion of cement pastes: 0% (control mix), 0.8 wt.% and 3.8 wt.% of binder (OPC + NS).
Deionised water was used as mixing water and nanosilica slurry was added to mix-
ing water prior to cement addition. The water content of the slurry was always ac-
counted for when fixing the water/binder ratio of the mixes. For safety precautions,
contact of nanosilica slurry with skin or eyes have been avoided, as well as circum-
stances that may cause a mist or spray of liquid or a dust of dried particles.
In several cases, a commercial superplasticizer (mainly based on a polyacrylic
type superplasticizer) in the form of an aqueous solution with a dry active matter
(SP) of 30 wt.% (superplasticizer density = 1.1 g/cm3; pH = 6.64) was also used. This
In order to investigate the effects of nanosilica addition on the flow and rheolog-
ical properties of cement pastes, the water demand (w/b ratio) of the mixes was first
evaluated at different workability (flow) levels by mini-slump tests. Next, rheomet-
ric tests on selected cement pastes were performed.
For mini-slump tests, each type of paste (0–3.8 wt.%NS) was prepared manually
by using 100 g of Portland or blended cement and different water/binder ratios, and
the mix workability was evaluated after 5 min of mixing through the use of a trun-
cated cone open at both ends (upper diameter = 20 mm; base diameter = 40 mm;
height = 60 mm) [31]. A similar test, based on a larger cone, has been standardised
for the measurement of cement mortar workability [32]. The area of the paste col-
lapsed without shocking, Acp (cm2), was measured by a planimeter and taken as a
measure of the mix workability. When no collapse occurred, the value of Acp was
about 12 cm2.
The changes in water demand of OPC and OPC–NS pastes produced by delayed
superplasticizer addition or by delayed addition of water aliquots (after the first
2 min of mixing) were also investigated.
In order to discriminate possible combined effects on mix workability exerted
by the addition of nanosilica and NaOH contained in the commercial NS slurry,
mini-slump tests on OPC pastes were performed by replacing an aliquot of mixing
water (deionized water) with an aqueous NaOH solution at pH = 10.2 (i.e. the pH of
the NS slurry, Table 2) or with 0.22 M NaOH solution, the latter corresponding to
the titrable alkali content of the slurry (0.56 wt.% as Na2O). The volume of mixing
water replaced by NaOH solution (10.4 cm3/100 g cement) corresponded to the vol-
ume of commercial slurry used to obtain a NS dose level of 3.8 wt.% in cement
pastes. The OPC pastes made with NaOH solution at pH = 10.2 or with 0.22 M NaOH
solution were designated as (OPC-NaOH)1 and (OPC-NaOH)2, respectively.
Finally, some mini-slump tests were performed on pastes made with quartzitic
sand in place of OPC. This sand (SiO2 = 91.3 wt.%) was preliminarily ground to ce-
ment fineness (ultra-fine quartzitic sand (UFQS): BET specific surface area 2 m2/g).
668 M. Berra et al. / Construction and Building Materials 35 (2012) 666–675

Table 3
Compositions of cement pastes designed for rheological tests and/or physico-mechanical characterisations.

Code Mix w/b SP dose level NS concentration in the liquid phase SP concentration in the liquid phase Workability
no. ratio (wt.%) (wt.%)a (wt.%)b (cm2)
1 OPC 0.30 – – – 16.6
2 OPC 0.36 – – – 59.4
3 OPC 0.50 – – – 227
4 OPC 0.30 0.33 – 1.09 152
5 OPC 0.30 0.66 – 2.15 186
6 OPC–0.8%NS 0.50 – 1.58 – 56.7
7 OPC–0.8%NS 0.75 – 1.06 – 184
8 OPC–0.8%NS 0.36 0.23 2.16 2.02 57.8
9 OPC–3.8%NS 0.50 – 7.06 – 13.9
10 OPC–3.8%NS 0.60 – 5.96 – 23.8
11 OPC–3.8%NS 0.75 – 4.82 – 55.7
12 OPC–3.8%NS 0.50 1.00 6.93 5.57 95
13 OPC–3.8%NS 0.36 1.32 9.24 7.49 56.7
14 OPC–3.8%NS 0.50 1.32 6.89 5.87 214
a
Calculated as: NS100/NS + w + SP.
b
Calculated as: SP100/NS + w + SP.

On the basis of the results of mini-slump tests, several types of cement pastes
were designed for the measurements of rheological properties and/or physico-
mechanical characterisations. Table 3 gives the w/b ratio, the superplasticizer dose
level, the NS and SP concentrations in the liquid phase, and the workability of the
cement pastes investigated.
Each paste was prepared with a mechanical mixer according to a three-step
procedure: (1) mechanical mixing for 2 min at 120 rpm, (2) hand mixing to break
up clumped cement particles (1 min), and (3) mechanical mixing for other 2 min
at 60 rpm. An aliquot of paste was immediately subjected to the rheometric test,
while the remaining portion was used, in most cases, to prepare cubic specimens
for the subsequent characterisation of hardened cement pastes.
The rheological tests were performed using a rheometer with a concentric cyl-
inder geometry, operating in controlled shear rate mode. For each test sample, a
shear stress (s) vs. shear strain rate (c_ ) curve with shear rates increasing from 0
to 150 s1 was first recorded (upper curve). Next, a down s  c_ curve was recorded
by reducing the shear rate from 150 s1 to 0. The yield stress, s0, and the plastic vis-
cosity, gp, of the test sample were calculated using the Bingham equation
(s ¼ s0 þ gp c_ ) and the down s  c_ curve in the shear rate range from 30 to
150 s1 [33].
Several stability tests were also performed on ‘‘simulated OPC–NS liquid
phases’’ that were obtained by adding different amounts of the concentrated nano-
silica slurry (30 wt.%NS) to a liquid sample resulting from the centrifugation (5 min
at 5000 rpm) of a fresh OPC paste with w/b = 0.50 (5 min of mixing). The chemical
composition of the centrifuged liquid sample was: Na+ = 18.9 mM; K+ = 33.3 mM;
Ca+2 = 20.8 mM; SO42 = 16.9 mM; pH = 13.1.
Stability tests were performed on the liquid samples containing different NS
concentrations (1.06, 1.58, 4.82 and 9.24 wt.%) in the absence or the presence of
superplasticizer (SP concentration in the liquid phase = 5.57 wt.%).
The final products resulting from NS sol destabilization (gel, flocculated parti-
cles, or milk-like suspension) were immediately centrifuged for 5 min at
5000 rpm, and then analysed by Differential Scanning Calorimetry (DSC) and Ther-
mogravimetric Analysis (TGA). A simultaneous thermoanalyzer TGA-DSC operating
in N2 atmosphere at a heating rate of 10 °C/min over a temperature range from 25
to 300 °C was used.
Finally, a sample of ultra-fine quartzitic sand (UFQS) was contacted with deion-
ized water for 1 h (liquid/solid ratio = 10 cm3/g), centrifuged for 5 min at 5000 rpm,
and then analysed by TGA/DSC. The centrifuged UFQS sample was taken as a refer-
ence material in evaluating the water retention capacity by NS sol destabilization
products.

2.2. Physical and mechanical tests on hardened cement pastes

Cubic specimens, 40-mm side, were cast from each paste investigated. After
24 h of curing within the moulds, the specimens were demoulded and cured in a
controlled temperature and humidity environment (20 °C and RH >95%).
After 7, 28 and 60 days of curing, three specimens of the same paste were char-
acterised for their compressive strength (Rc), dry and ssd (saturated surface-dried)
densities, and total porosity.
The Rc measurements were performed according to UNI-EN 196–1. The total
porosity was evaluated from measurements of water absorption and dry density,
the latter being determined from the dimensions and weight of the specimens after
drying at 105 °C.
2.3. Stability tests on nanosilica slurries
In order to elucidate the mechanisms by which the addition of nanosilica pro-
duces a considerable increase in the water demand of cementitious mixes, stability
tests on slurries containing different concentrations of nanosilica (1.06–30 wt.%NS)
were performed. Six NS concentrations were tested: 1.06, 1.58, 4.82, 7.06 and
9.24 wt.% corresponding to those of the paste Nos. 7, 6, 11, 9 and 13 in Table 3,
and 30 wt.% corresponding to the concentrated NS slurry (Table 2). These slurries
were obtained by diluting the concentrated NS slurry with appropriate amounts
of deionised water.
The tendency of each slurry to form a gel (a three-dimensional network
throughout the slurry), flocculated particles (flocs) or stable milk-like suspension,
was evaluated when different amounts of individual chemical species (sodium
hydroxide, calcium hydroxide, or superplasticizer) were added in the form of aque-
ous solutions (NaOH 5 M, saturated Ca(OH)2 solution, or 30 wt.% SP) to 50 ml of a
specific slurry. In the case of NaOH or Ca(OH)2 addition, the instability of a specific
slurry (sol destabilisation) was evaluated in terms of the pH value at which gelation
or coagulation occurred. In the case of superplasticizer addition, the instability of a
specific slurry was evaluated in terms of the SP concentration responsible for sol
destabilisation (formation of milk-like suspension).
3. Results and discussion
3.1. Characterisation of nanosilica sample
Fig. 1a and b shows, respectively, the TEM image and the EDS
analysis of dry nanosilica samples.
The TEM image revealed that the silica nanoparticles were char-
acterised by a spherical shape and a narrow size range (5–20 nm),
with an average size of 10.5 ± 2.3 nm (numerical image analyses
carried out by iTEMÒ Soft Imaging System) and no tendency to coa-
lescence. The BET specific surface area was 345 m2/g (Table 2) and
this value was consistent with the geometric sizes of silica
nanoparticles.
The EDS profile (Fig. 1b) showed essentially the peaks corre-
sponding to the following four elements: Si, O, C, and Cu. Both Si
and O peaks corresponded to SiO2, while the dominant peaks orig-
inated from copper and carbon were due to TEM copper grid and
graphite coating.
Chemical analysis indicated that dry nanosilica was essentially
composed of SiO2 (98.1 wt.%) accompanied by a low amount of so-
dium (1.86 wt.% as Na2O), sulphate (0.02 wt.% as SO3) and chloride
(0.006 wt.%). The sodium content of dry NS resulted essentially
from the sodium hydroxide used for stabilizing nanosilica slurry.
As shown in Table 4, the average particle size of the nanosilica
tested in this work was near the lowest size investigated by other
researchers.
 M. Berra et al. / Construction and Building Materials 35 (2012) 666–675
TEM image
(a)
Fig. 1. TEM image (a) and EDS profile (b) of nanosilica particles.
Table 4
Average particle sizes of nanosilica investigated by other researchers.
Average particle size (nm) Reference
5 [9]
9 [25], [27]
10 [8], [12], present study
15 [11], [14], [16], [19], [29], [30]
20 [11], [13], [15], [21], [26], [28]
30 [11], [21], [26], [28]
40 [18]
50 [10], [20]
80 [29]
120 [21], [26], [28]
3.2. Water demand and rheological behaviour of cement pastes
Fig. 2a–c shows the results of mini-slump tests on all the types
of cement pastes investigated. In this figure, the effects of increas-
ing the w/b ratio or the NS content, as well as the influence of
NaOH addition on the workability of cement pastes containing or
not containing superplasticizer are shown. The mix workability
was evaluated in terms of the area Acp (cm2) of the collapsed
sample.
The addition of nanosilica slurry to OPC pastes always reduced
the mix workability and this reduction was pronounced for the
OPC-3.8%NS pastes made without superplasticizer (Fig. 2a). For
such mixes, it was necessary to use w/b ratios above 0.40 to trans-
form the mixture from humid earth to viscous paste, and the sticky
aspect of this paste disappeared only when the w/b ratio was raised
above 0.55–0.60. Depending on the workability level requested,
percentage water demand increases of 100–115% were recorded.
As shown in Fig. 2b, in the case of OPC pastes, no appreciable
difference in mix workability was found when the mixing water
(deionized water) was partially replaced by an aqueous NaOH
solution at pH = 10.2 ((OPC-NaOH)1 paste) or by 0.22 M NaOH
solution ((OPC-NaOH)2 paste). This comparison proved that, at a
fixed w/b ratio (w/b = 0.40 or 0.45), the much lower workability
of OPC-3.8%NS pastes was not attributable to the amount of NaOH
added to the mixing water (10.4 cm3 NaOH solution/100 g cement;
NaOH concentration in the mixing water of 0.051 or 0.057 M)
through the NS slurry. On the other hand, the addition of NaOH
to OPC pastes is known to cause marked changes in rheological,
microstructural and mechanical properties of the cement pastes
only when NaOH is added to the mixing water at much higher con-
centration levels (0.5–4.5 M) [34,35].
669
EDS profile
(b)
As shown in Fig. 2c, at a fixed w/b ratio, the addition of superp-
lasticizer always increased the workability of the cement pastes,
and the gain in workability was found to be strongly dependent
on the NS content, SP dose level and w/b ratio of the mixes.
With the use of appropriate dose levels of superplasticizer it
was possible to eliminate the adverse effect of nanosilica on the
workability of cement pastes. Thus, for example, SP dose levels of
0.23 wt.% for OPC-0.8%NS mix and 1.32 wt.% for OPC–3.8%NS mix
(Fig. 2b) were appropriate to achieve the same workability (57–
59 cm2) as that of the OPC paste (control) (Fig. 2a) without chang-
ing the water/binder ratio (w/b = 0.36). These two SP dose levels
did not significantly change if a higher workability level for the
three types of paste was considered (Acp = 227 cm2; w/b = 0.50).
The data in Fig. 2a and c were used for designing the composi-
tions of the cement pastes (Table 3) to be subjected to subsequent
rheological tests and/or physico-mechanical characterisations.
Fig. 3 shows the effect of delayed additions of mixing water ali-
quots, Dw0 /b, on the workability of the OPC and OPC–3.8%NS mixes
made without superplasticizer and with a w/b ratio of 0.50 or 0.75
(w/b = w0/b + Dw0 /b in case of delayed water aliquot addition). In
the case of the OPC pastes, a w/b ratio of 0.35 was also used yield-
ing the same workability (Acp  55 cm2) as that of the OPC–3.8%NS
paste with w/b = 0.75 and Dw0 /b = 0 (immediate mixing water
addition).
Irrespective of the w/b ratio tested, no gain in workability was
recorded for the OPC pastes when the addition of water aliquots
was delayed. Conversely, for the OPC–3.8%NS mixes made with a
w/b ratio of 0.75, a significant gain in workability was achieved
by delaying the addition of water aliquots. Over the range of
Dw0 /b values from 0 (immediate addition) to 0.35, the mix work-
ability increased almost linearly with increasing Dw0 /b up to reach-
ing a high Acp value (200 cm2). This Acp value was much higher than
that measured in the case of immediate water addition
(Acp = 55.7 cm2) but was well below the Acp value (314 cm2) exhib-
ited by the OPC paste with the same w/b ratio (w/b = 0.75).
If the w/b ratio of the OPC–3.8%NS pastes was reduced from
0.75 to 0.50, the gain in workability associated with delayed water
additions became less significant: the area Acp increased from 14 to
30 cm2 as Dw0 /b was increased from 0 to 0.25. So, the workability
of this mix remained well below the Acp value (227 cm2) measured
for the OPC paste with w/b = 0.50. In every case, the delayed addi-
tion of mixing water aliquot appeared to be an effective way of
reducing the adverse effect of nanosilica on mix workability with-
out changing the w/b ratio and/or adding superplasticizer.
670 M. Berra et al. / Construction and Building Materials 35 (2012) 666–675

Effect of w/b ratio Effect of NaOH addition

(a) 350 OPC
(b) 140
300
OPC-0.8%NS
120
250
OPC-3.8%NS 100
A cp (cm )
2

200

A cp (cm )
80

2
150 60
100 40

50 20

0 0
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
w/b ratio

Effect of superplasticizer addition

300
(c) OPC (w/b = 0.30)
250 OPC-0.8% NS (w/b = 0.36)

OPC-0.8% NS (w/b = 0.50)

200
Acp (cm )

OPC -3.8% NS (w/b = 0.36)

2

OPC-3.8% NS (w/b = 0.50)

150

100

50

0
0.0 0.5 1.0 1.5 2.0 2.5
SP dose level (wt.%)

Fig. 2. Results of mini-slump tests on all the types of cement paste investigated: effects of water/binder ratio (a), NaOH (b) and superplasticizer (c) on the mix workability.

pronounced effect of nanosilica on the plastic viscosity of mortar

350 samples was reported.
The addition of superplasticizer to OPC pastes (paste Nos. 1, 4
300 and 5; w/b = 0.30) or to OPC–3.8%NS (paste Nos. 9, 12 and 14; w/
b = 0.50) always produced a remarkable reduction in both the yield
250
stress (from 52–76 to 2–16 Pa) and the plastic viscosity (from 0.95–
0.29 to 0.057–0.061 Pa s) (Fig. 4b), as a result of the development of
dispersive forces (electrostatic repulsion and steric hindrance) orig-
Acp (cm )
2

200
inated by superplasticizer adsorption upon cement particles. In
qualitative terms, adding superplasticizer (Fig. 4b) was equivalent
150 OPC (w/b = 0.35) to increasing the w/b ratio of cement pastes (OPC paste Nos. 1, 2
OPC (w/b=0.50) and 3; OPC–3.8%NS paste Nos. 9, 10 and 11) (Fig. 4c).
100 Fig. 5 compares the results of mini-slump and rheological tests
OPC (w/b = 0.75)
in terms of the area Acp of collapsed paste against its yield stress, s0
50 OPC-3.8%NS (w/b=0.50) or its plastic viscosity, gp.
OPC-3.8%NS (w/b=0.75) As can be noted, there was a good power relationship between
0 s0 and Acp or between gp and Acp. According to these relationships,
0 0.1 0.2 0.3 0.4 0.5 no collapse of cement paste (Acp = 12.4 cm2) in the mini-slump test
Δ w'/b would be associated with plastic viscosity and yield stress values
above approx. 0.93 Pa s and 75 Pa, respectively.
Fig. 3. Effect of delayed addition of mixing water aliquots on the workability of
cement pastes incorporating nanosilica.

3.3. Interaction between silica nanoparticles and some chemical

species dissolved in the liquid phase of fresh cement pastes
Fig. 4a–c shows the results of the rheological tests on the ce-
ment pastes made with different nanosilica content, superplasti- The remarkable increase in water demand produced by nanosil-
cizer dose level, or w/b ratio. ica addition to cement pastes (Fig. 2a and c), as well as the exis-
In the absence of superplasticizer, the addition of nanosilica to tence of a beneficial effect of delayed additions of mixing water
cement pastes (paste Nos. 3, 6, and 9 in Table 3; w/b = 0.50) pro- aliquots on the workability of cement pastes incorporating NS
duced a considerable increase in both the yield stress, s0 (from 9 (Fig. 3) suggested that the marked increase in the yield stress
to 76 Pa) and the plastic viscosity, gp (from 0.018 to 0.29 Pa s) and plastic viscosity produced by nanosilica addition (Fig. 4a and
(Fig. 4a). These results were consistent with those reported for ce- b) could not be explained by the only formation of a denser packing
ment mortars by other researchers [17,25], although a less of solid particles in the mixtures incorporating NS [25]. A strong
 M. Berra et al. / Construction and Building Materials 35 (2012) 666–675 671

Effect of nanosilica content 80 1

(a) 80 0.4
yield stress OPC
70 0.9
70 OPC-0.8%NS
0.3 plastic viscosity
OPC-3.8%NS 0.8
60 0.3 60
OPC 0.7
50

ηp (Pa s)
τo (Pa)

0.2 50 OPC-0.8%NS
OPC-3.8%NS 0.6
40

ηp (Pa s)
τ0 (Pa)
0.2 40 0.5
30
yield stress 0.1 0.4
20 30
plastic viscosity
0.1 0.3
10
20
0 0.0 0.2
0 1 2 3 4 10
0.1
NS dose level (wt.%)
0 0
0 50 100 150 200 250
Effect of superplasticizer content 2
(b) 80 1 A cp (cm )
OPC (w/b=0.30)
70 0.9
OPC-3.8%NS (w/b=0.50)
0.8 Fig. 5. Relationship between the yield stress or plastic viscosity and the area of
60 collapsed paste Acp in the mini-slump test.
0.7
50 yield stress
ηp (Pa s)
0.6
τo (Pa)

40 plastic 0.5 300

viscosity
30 0.4
w/s = 0.40
0.3 250
20
0.2
10 200
Acp (cm2)
0.1
0 0
0.0 0.5 1.0 1.5 2.0 2.5 150 OPC

SP dose level (wt.%) UFQS

100
UFQS (pH = 10.3)
Effect of water/binder ratio
80 1 50
(c) 0.9
70
0
0.8 0 1 2 3 4
60
0.7
NS dose level (wt.%)
50
ηp (Pa s)

0.6
τo (Pa)

40
30
20
10
0 0
0.2 0.3 0.4 0.5 0.6 0.7 0.8
Fig. 4. Effects of NS dose level (a), SP dose level (b) and w/b ratio (c) on the yield
stress and plastic viscosity of OPC and OPC–NS pastes.
and ‘‘instantaneous’’ interaction between silica nanoparticles and
some chemical species dissolved in the liquid phase of fresh ce-
ment pastes, with formation of destabilisation products character-
ised by high water retention capacity, should be hypothesised to
explain the flow and rheological properties of OPC–NS pastes. Such
a hypothesis was supported by the results of mini-slump tests on
the pastes made with ultra-fine quartzitic sand and, even more,
by the results of stability tests on the slurries containing different
NS concentrations.
Fig. 6 compares the effect of nanosilica addition on the work-
ability of OPC or ultra-fine quartzitic sand (UFQS) pastes made
without superplasticizer, at a fixed water/solid ratio (w/s = 0.40).
In the absence of nanosilica, similar workabilities (Acp = 104–
105 cm2) were measured on the two types of pastes. Differently
from what was observed for OPC pastes (great workability reduc-
tion) and in spite of the much higher specific surface area of nano-
silica (345 m2/g) as compared to UFQS sample (2 m2/g), the partial
0.5 Fig. 6. Effect of nanosilica addition on the workability of OPC or ultra-fine quartzitic
0.4 sand (UFQS) pastes.
0.3
0.2
0.1 replacement of sand with nanosilica greatly increased the work-
ability of the UFQS pastes (Acp = 280 cm2 for UFQS–3.8%NS against
104 cm2 for UFQS paste without nanosilica). As discussed later, the
different effect of nanosilica on the workability of OPC and UFQS
pastes was related to its different interaction with the liquid phase
of the two kinds of paste.
Fig. 7 shows the effect of separate additions of sodium hydrox-
ide and calcium hydroxide on the stability of slurries containing
different concentrations of nanosilica (1.06–30 wt.%). In discussing
these results, the stability (or the instability) of the various slurries
subjected to NaOH addition was also related to the flow properties
(Acp values) of the corresponding OPC–NS pastes without superp-
lasticizer (Table 3).
The addition of NaOH was found to cause instantaneous forma-
tion of a stable gel in the slurries with NS concentrations ranging
from 1.58 to 30 wt.%. No sol destabilisation was observed in the
slurry containing 1.06 wt.%NS (OPC–0.8%NS paste with w/
b = 0.75; Acp = 184 cm2), at least up to the highest pH value inves-
tigated (pH = 13.5). The pH of incipient gelation, pHig, increased
with decreasing NS concentration, especially over the range of NS
contents from 7.06 to 4.82 wt.%. The value of pHig was 10.4 for
the concentrated NS slurry (30 wt.%) and increased to 11.0 and
13.0 for the slurries containing 7.06 and 4.82 wt.%NS, respectively.
The last two NS concentrations corresponded, respectively, to
those of the OPC–3.8%NS pastes with w/b = 0.50 (Acp = 13.9 cm2)
672 M. Berra et al. / Construction and Building Materials 35 (2012) 666–675
Fig. 7. Results of stability tests on nanosilica slurries.
or w/b = 0.75 (Acp = 55.7 cm2). The amount of gel formed increased
with increasing NS concentration and, to a minor extent, with
increasing pH above pHig.
In the case of Ca(OH)2 addition, no gel was formed in all of the
slurries investigated. However, rapid coagulation of colloidal parti-
cles was observed in the slurries with NS concentrations ranging
from 1.06 to 7.06 wt.%. The pH of incipient coagulation, pHic, was
little affected by the NS concentration and slightly increased from
10.95 (1.06 wt.%NS) to 11.3 (7.06 wt.%NS). The amount of floccu-
lated particles (white flocs) first significantly increased and then
decreased with increasing NS concentration (maximum amount
of flocs in the slurry with NS concentration of 4.82 wt.%). Thus,
no effective coagulation of colloidal particles was observed in the
slurries with the NS concentrations of 9.24 and 30 wt.%, at least
up to the highest pH value (pH = 11.5) reached with the use of a
saturated Ca(OH)2 solution. In these two slurries, instantaneous
formation of flocs was locally observed during Ca(OH)2 addition,
but these flocs disappeared rapidly under intense agitation.
The separate addition of superplasticizer to the NS slurries al-
ways led to the instantaneous formation of a stable milk-like sus-
pension. The concentration of superplasticizer needed for the NS
sol destabilisation was always low (SP concentration in the liquid
phase = 0.13–0.18 wt.%) and virtually independent of the NS con-
centration tested. Increasing SP concentration in the slurry up to
5.60 wt.%, did not produce flocculation of colloidal particles but re-
sulted in an increased colour intensity of the suspension, especially
for the slurries with higher NS concentrations.
The transformation of all NS slurries into stable milk-like sus-
pensions was not attributable to the slight reduction of the slurry
pH produced by superplasticizer addition (final pHs of 9.0–9.2
against the initial slurry pHs of 10.0–10.2). This phenomenon could
be ascribed to a micellar transformation of silica nanoparticles in-
duced by superplasticizer addition, with formation of larger colloi-
dal particles characterised by a lower reactivity. This fact should be
remembered when using superplasticizer to improve the workabil-
ity of cementitious mixes incorporating nanosilica. In this regard,
there is a lack of information about the exact procedures followed
in the preparation of cementitious mixes incorporating both nano-
silica and superplasticizer, especially when nanosilica is used in
the form of a slurry.
In the light of the results of this study, the procedure of adding
superplasticizer to mixing water containing nanosilica prior to ce-
ment addition (immediate superplasticizer addition) appears to be
inappropriate. On the other hand, if the addition of superplasticizer
to the cementitious mix is delayed, there is much greater difficulty
to uniformly disperse the mix ingredients, as a consequence of the
instantaneous formation of gels from NS sol destabilisation.
This was supported by the results of the stability tests on ‘‘sim-
ulated OPC-NS liquid phases’’. These tests showed that, in the
700
600
water content, wc (wt. %)
500
400
300
200
100
0
0 1 2 3 4 5 6 7 8 9 10
NS concentration in the OPC liquid phase (wt. %)
Fig. 8. Water content of centrifuged gels as a function of the NS concentration in
the simulated OPC–NS liquid phases.
absence of superplasticizer, gel was formed instantaneously in all
samples investigated exception made for the lowest NS concentra-
tion (1.06 wt.%). Visually, the amount of gel increased with increas-
ing NS concentration, and the addition of superplasticizer (SP
concentration in the liquid phase = 5.57 wt.%) was not able to
destabilise the gel formed in the samples with NS concentrations
above 7.06 wt.%.
It follows that, in the case of preparation of cementitious mixes
incorporating nanosilica, delayed superplasticizer addition and
appropriate mixer should be adopted.
Fig. 8 shows the changes in the water content, wc, of the centri-
fuged gels as a function of the NS concentration in the ‘‘simulated
OPC–NS liquid phases’’ not containing superplasticizer.
As can be noted, over the range of NS concentration tested
(1.58–9.24 wt.%), the water content of the gels, as determined by
TGA analysis, was always high and greatly increased with increas-
ing NS concentration (wc = 150–572 wt.% of dry solid).
Table 5 compares the water contents (wc) of the centrifuged gels
resulting from the destabilisation of the simulated OPC-NS liquid
phases containing 9.24 wt.%NS, in the absence or the presence of
superplasticizer (SP concentration in the liquid phase = 5.57 wt.%).
This table also gives the wc values exhibited by the centrifuged
UFQS sample (taken as a reference material) and by the solid sam-
ples resulting from the centrifugation of the nanosilica slurries
(9.24 wt.%NS) destabilised by separate NaOH (gel formation) or
superplasticizer (milk-like suspension) addition.
The wc values for the three centrifuged gels (wc = 507–700 wt.%
of dry solid) were always much higher than the ones exhibited by
the centrifuged milk-like suspension (wc = 155 wt.% of dry solid)
and, even more, by the centrifuged sample of ultra-fine quartzitic
sand (wc = 39 wt.% of dry solid). Moreover, the water content of
the centrifuged gels was reduced by superplasticizer addition.
Fig. 9 shows the DSC thermograms of the centrifuged solids de-
scribed in Table 5.
These thermograms revealed a great difference between the
water retention capacities by the ultra-fine sand and the gels
formed from NS sol destabilisation. In the case of the ultra-fine
sand, the loss of water occurred totally at temperatures below
100 °C (peak temperature = 80 °C), and this behaviour was typical
of unbound water. A similar thermal behaviour was also recorded
for the solid sample obtained from centrifugation of the NS slurry
destabilised by superplasticizer addition (milk-like suspension).
Conversely, the loss of water from the three centrifuged gels
mostly occurred at temperatures above 100 °C, and the peak tem-
perature ranged from 120 to 135 °C, depending on the type of gel
 M. Berra et al. / Construction and Building Materials 35 (2012) 666–675 673

Table 5
Water contents of NS sol destabilisation products.

Liquid phase NS concentration in the liquid Destabilizing Gel Milk-like Water content of centrifuged solid sample
phase (wt.%) agent suspension (wt.% of dry solid)
Simulated OPC–NS 9.24 – X 572
Simulated OPC–NS–SP 9.24 – X 507
NS slurry 9.24 NaOH X 700
NS slurry 9.24 SP X 155
Ultra-fine quartzitic sand 39

formation was possible since the pHs (10.1–10.3) were well below
the corresponding pHig values (above 10.9) (Fig. 7). Consequently,
no workability reduction was produced by NS addition. Indeed, a
remarkable increase in workability was observed, especially for
the UFQS–3.8%NS mix. This fluidising effect was not attributable
to an interaction between the siliceous sand particles and the so-
dium hydroxide contained in the NS slurry, since no change in
workability was observed when the UFQS paste was made without
NS (w/s = 0.40) and deionised water preliminarily added with
NaOH (up to pH = 10.3) was used as mixing water, in place of
deionised water alone. The improved workability of the sand
pastes incorporating NS could be related to an enhancement of
the repulsion forces between the sand particles as a result of NS
adsorption upon such particles.

3.4. Compressive strength development of cementitious mixes

Fig. 9. DSC thermograms of the centrifuged solids described in Table 5.
formed. In every case, the water retained by these gels was mostly
in the form of bound water.
Thus, the high wc values measured on the centrifuged gels were
primarily attributable to the strong chemical interaction between
water and destabilised NS sol and, secondarily, to their higher spe-
cific surface area as compared to ultra-fine quartzitic sand.
The instantaneous and abundant formation of gels character-
ised by high water retention capacities may explain the consider-
able increase in both yield stress and plastic viscosity (Fig. 4a
and b) and, consequently, the high water demand produced by
the addition of nanosilica to cementitious mixes (Figs. 2a and c).
Such a chemical interaction may also explain the observed benefi-
cial effect of delayed additions of mixing water aliquots on the
workability of OPC–NS mixes (Fig. 3), as well as the opposite effects
exerted by nanosilica addition on the flow properties of cement or
ultra-fine sand (UFQS) pastes (Fig. 6). In particular, for the UFQS
pastes tested (w/s = 0.40; NS dose level = 0.8 or 3.8 wt.% of sand;
NS concentration in the liquid phase = 2.0 or 9.5 wt.%), no gel
In order to correctly evaluate the effect of nanosilica addition on
the mechanical strength development of cementitious materials,
all of the test mixes should be made with the same water/binder
ratio and the same workability. However, due to the high water de-
mand of nanosilica, these two test conditions are difficult to satisfy
at the same time, especially if relatively high dose levels of nano-
silica are tested and no superplasticizer is used. On the other hand,
the addition of superplasticizer may significantly affect both the
cement hydration and the stability of NS sols, thus altering the ac-
tual effect of nanosilica on strength development.
Therefore, in the present work, the effect of nanosilica addition
on the compressive strength development of OPC pastes was eval-
uated under the following three different test conditions: (1) at the
same water/binder ratio (w/b = 0.50) but different workability
(paste Nos. 3, 6, and 9), (2) at the same workability (Acp = 55–
59 cm2) but different w/b ratio (paste Nos. 2, 6, and 11 in Table
3), and (3) at the same water/binder ratio (w/b = 0.36) and the
same workability (Acp = 57–59 cm2), the latter being achieved
through appropriate addition of superplasticizer to OPC–0.8%NS
(SP = 0.23 wt.%) and OPC–3.8%NS mixes (SP = 1.32 wt.%) (paste
Nos. 2, 8, and 13). The effect of superplasticizer addition on the

Table 6
Compressive strength and total porosity values for the three types of cement pastes made with the same workability or the same w/b ratio.

Mix w/b ratio SP (wt.%) Acp (cm2) Rc (N/mm2) Total porosity (%)
Age (days) Age (days)
7 28 60 7 28 60
OPC 0.50 – 227 18.8 28.0 28.5 44.0 44.1 44.0
OPC–0.8%NS 0.50 – 56.7 20.2 27.7 29.4 45.1 44.0 43.2
OPC–3.8%NS 0.50 – 13.9 21.1 25.6 29.2 45.2 46.1 44.3
OPC 0.36 – 59.4 43.1 49.4 55.6 38.0 35.1 31.1
OPC–0.8%NS 0.50 – 56.7 20.2 27.7 29.4 45.1 44.0 43.2
OPC–3.8%NS 0.75 – 55.3 8.3 11.5 12.2 58.2 57.2 55.2
OPC 0.30 – 16.6 56.1 58.3 68.0 31.0 28.0 24.0
OPC 0.30 0.66 186 55.5 62.4 70.6 31.0 27.0 24.0
OPC–3.8%NS 0.50 – 13.9 21.1 25.6 29.2 45.2 46.1 44.3
OPC–3.8%NS 0.50 1.00 95.0 28.9 32.8 36.3 49.0 46.2 45.0
674 M. Berra et al. / Construction and Building Materials 35 (2012) 666–675

strength development was evaluated through Rc measurements on
additional pastes of OPC and OPC–3.8%NS (paste Nos. 4 and 12).
Table 6 summarises the compressive strength and total porosity
data relative to the three types of cement paste made with the
same w/b ratio (point (1)) or the same workability (point (2)), after
7, 28 and 60 days of curing at 20 °C and RH >95%.
Fig. 10a and b shows, respectively, the unconfined compressive
strengths (plus Standard Deviation) and the total porosities of the
three types of cement pastes made with the same w/b ratio and the
same workability level (point (3)).
As shown in Table 6, when the cement pastes were made with
the same w/b ratio (w/b = 0.50) but different workability level (Acp
decreased from 227 to 13.9 cm2 as the NS dose level was increased
from 0 to 3.8 wt.%), there existed no appreciable difference be-
tween the Rc values exhibited by the three types of paste, at least
up to the ultimate curing time investigated (60 days). Due to the
relatively high w/b ratio adopted to avoid the use of superplasticiz-
er in the mixes incorporating NS, the three types of paste were
characterised by relatively high porosities (43.2–44.3% after
60 days curing) and, consequently, by relatively low compressive
strengths (28.5–29.2 MPa).
If the three types of paste were made without superplasticizer,
with the same workability level (Acp = 55–59 cm2) and different w/
b ratios, a considerable reduction of compressive strength was ob-
served as the nanosilica dose level was increased from 0 to 3.8 wt.%
(at 60 days, Rc decreased from 55.6 to 12.2 MPa). This Rc reduction
was attributable to the high water demand of the nanosilica and,
consequently, to the much higher w/b ratio used for the mixes
incorporating NS (w/b = 0.75 for OPC–3.8%NS, and w/b = 0.50 for
OPC–0.8%NS against w/b = 0.36 for OPC paste).
As shown in Fig. 10a, a beneficial effect, not important but
potentially imputable to nanosilica on strength development,
was observed when the three types of pastes were made with
the same workability (Acp = 57–59 cm2) and the same w/b ratio
(w/b = 0.36), and nanosilica was used at a dose level of 3.8 wt.%.
Under these testing conditions, a strength gain of 17.4% after
28 days of curing was recorded but this gain reduced to 7.6% after
60 days. The Rc values (42–55 MPa for OPC and 50–60 MPa for
OPC–3.8%NS) were consistent with the corresponding values of
the total porosity (38–30% for OPC and 34–29% for OPC–3.8%NS)
(Fig. 10b) and were also congruent with the data of Table 6 relative
to the three types of paste made with a higher w/b ratio (w/
b = 0.50).
However, it must be remembered that the OPC–NS mixes of
Fig. 10a were obtained through the use of appropriate amounts
of superplasticizer (SP = 0.23 wt.% for OPC–0.8%NS and 1.32 wt.%
for OPC–3.8%NS).
As shown in Table 6, the addition of superplasticizer to OPC
pastes (w/b = 0.30; SP = 0.66 wt.%) or to OPC–3.8%NS pastes (w/
b = 0.50; SP = 1.0 wt.%) produced a strength gain of 6.9% for OPC
and 27% for OPC–3.8%NS after 28 days of curing. On the basis of
the comparable porosity values exhibited by the mixes containing
or not containing superplasticizer (Table 6), and taking in mind
that the commercial superplasticizer used in this study is well
known as an accelerating admixture for cement hardening, the ob-
served strength gain has to be mostly ascribed to an accelerating
effect of such superplasticizer on cement hardening. Thus, the ac-
tual contribution of nanosilica to strength gain (Fig. 10a) must be
quantitatively assessed as low.

4. Conclusions
Compressive strength
(a) 70 The addition of nanosilica to cementitious mixes produces a
w/b = 0.36 remarkable reduction of the mix workability, due to instantaneous
2
60 A cp = 57-59 cm
interactions between the nanosilica sol and the liquid phase of the
S.D.
50 S.D.
4.7
cementitious mixes (mainly dissolved alkalis), with formation of
4.0 S.D.
Rc (MPa)

S.D. gels characterised by high water retention capacities.

40 2.7
S.D.
S.D. 1.8 S.D. OPC
S.D. S.D. 1.2
2.6
3.9 The delayed addition of mixing water aliquots proves to be an
30 0.5 2.5
OPC-0.8%NS
effective way of reducing the adverse effect of nanosilica on mix
0.23%SP workability, without changing the water/binder ratio and/or add-
20
OPC-3.8%NS ing superplasticizer. In contrast, no workability improvement asso-
1.32%SP
10 ciated with delayed water addition is observed for Portland cement
mixes.
0
7 28 60 In the case of using superplasticizer to improve mix workability,
age (days) the procedure of adding superplasticizer to the mixing water con-
taining nanosilica prior to cement addition (immediate superplast-
icizer addition) appears to be inappropriate, due to the
Total porosity
50 instantaneous interaction between superplasticizer and nanosilica
(b) w/b = 0.36 that reduces nanosilica reactivity. On the contrary, a delayed addi-
2
A cp = 57-59 cm tion of the superplasticizer, coupled with the use of an appropriate
total porosity (%)

40
mixer for the break down of the gels formed from nanosilica sol
30
destabilisation, proves to be the best procedure to uniformly dis-
OPC perse the mix ingredients, without significantly penalising the
nanosilica reactivity.
20 OPC-0.8%NS
0.23%SP The results from mechanical tests suggest that, because of the
OPC-3.8%NS water retention in the NS containing mixes and the consequent
10 1.32%SP need of increasing the w/b ratio to obtain a proper workability, it
is not correct to compare Rc data with conventional OPC at the
0 same w/b ratio. The proper comparison must be carried out be-
7 28 60
tween mixes with the same workability and the same w/b ratio,
age (days) obtained by adding superplasticizers. The comparison in this case
Fig. 10. Compressive strengths (a) and total porosities (b) of OPC and OPC–NS
shows a limited increase of Rc for samples containing nanosilica,
pastes made with the same w/b ratio and the same workability level. Standard to be attributed mostly to the accelerating effect of superplasticizer
deviation (SD) for Rc measurements is also given. on cement hardening.
 M. Berra et al. / Construction and Building Materials 35 (2012) 666–675
Thus, only a limited quote of the improvement in compressive
strength of cementitious mixes can be ascribed to nanosilica addi-
tion, at least when this admixture is used in the form of a slurry
(mean particle size = 10 nm; sodium hydroxide as stabilising
agent) at NS dose levels up to 3.8 wt.% of blended cement.
Acknowledgement
This work has been financed by the Research Fund for the Ital-
ian Electrical System under the Contract Agreement between RSE
(formerly known as ERSE) and the Ministry of Economic Develop-
ment - General Directorate for Nuclear Energy, Renewable Energy
and Energy Efficiency, stipulated on July 29, 2009 in compliance
with the Decree of March 19, 2009.
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