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Construction and Building Materials 96 (2015) 508517

Contents lists available at ScienceDirect

Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Experimental study of the mechanical properties and durability

of self-compacting mortars with nano materials (SiO2 and TiO2)
S. Rao a, P. Silva b, J. de Brito c,
a

Structures Division, Department of Civil Engineering, National Institute of Technology, Warangal, India
CERis-ICIST, Instituto Superior de Engenharia de Lisboa (ISEL - IPL), R. Conselheiro Emdio Navarro, 1, 1959-001 Lisbon, Portugal
c
CERis-ICIST, Instituto Superior Tcnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal
b

h i g h l i g h t s

Updated research on the application of nano materials (SiO2 and TiO2) in the production of self-compacting mortars.

Feasibility analysis of nano materials in self-compacting mortars mixes.

Analysis of the properties of self-compacting mortars with nano materials in fresh and hardened states.

Compressive and flexural strength, porosity, water absorption and carbonation penetration are discussed.

a r t i c l e

i n f o

Article history:
Received 12 June 2015
Received in revised form 28 July 2015
Accepted 9 August 2015

Keywords:
Self-compacting mortar
Fly ash
Nano titanium
Nano silica
Fresh properties
Mechanical properties
Durability

a b s t r a c t
Cement, as well as the remaining constituents of self-compacting mortars, must be carefully selected, in
order to obtain an adequate composition with a granular mix as compact as possible and a good
performance in the fresh state (self-compacting effect) and the hardened state (mechanical and
durability-related behavior). Therefore in this work the possibility of incorporating nano particles in
self-compacting mortars was studied. Nano materials are very reactive due mostly to their high specific
surface and show a great potential to improve the properties of these mortars, both in mechanical and
durability terms.
In this work two nano materials were used, nano silica (nano SiO2) in colloidal state and nano titanium
(nano TiO2) in amorphous state, in two types of self-compacting mortars (ratio binder:sand of 1:1 and
1:2). The self-compacting mortar mixes have the same water/cement ratio and 30% of replacement of
cement with fly ashes. The influence of nano materials nano-SiO2 and nano-TiO2 on the fresh and hardened state properties of these self-compacting mortars was studied. The results show that the use of nano
materials in repair and rehabilitation mortars has significant potential but still needs to be optimized.
2015 Elsevier Ltd. All rights reserved.

1. Introduction
Fly ash (FA) is one of the most used industrial wastes in the
cement and concrete industry as an addition and they have many
advantages, such as a reduction of cement consumption, an
increase of concretes workability, and a potential increase of concretes durability and mechanical strength at later ages. However,
the retarding effect on the evolution of mechanical strength in
the first ages may, in some cases, represent a significant drawback.
Even though this effect may be favorable for some applications,
such as casting of large volume elements [1], in most cases the
effect is uncalled for. In order to compensate it many methods have
Corresponding author.
E-mail address: jb@civil.ist.utl.pt (J. de Brito).
http://dx.doi.org/10.1016/j.conbuildmat.2015.08.049
0950-0618/ 2015 Elsevier Ltd. All rights reserved.

been experimented to accelerate the hydration process in the early

ages in binary mixes of cement and fly ash including grinding processes of the components [2], chemical activation of the fly ash [3],
hydrothermal treatments [4,5], among others.
Recently nano silica (nano-SiO2) was introduced in the study of
mortars and/or concrete and various studies have demonstrated
that, even at small contents, it can improve the mechanical properties of these cementitious mixes [6]. According to Nazari and Riahi
[1], it was possible to increase the compressive strength by 70%
with the addition of 4% of nano-SiO2 (in cement mass). Similarly
Shih et al. [6] demonstrated that an addition of 0.6% of colloidal
nano-SiO2 can increase the compressive strength of cement pastes
by 43.8%. Li et al. [7] refer that, with the addition of 3% and 5% of
SiO2 in cement-based mortars, the 28-day compressive strength
increases by 13.8% and 17.5% respectively. Zhang et al. [2] e Li

S. Rao et al. / Construction and Building Materials 96 (2015) 508517

et al. [7] refer significant improvements of the mechanical properties of cementitious mixes with large replacement of cement with
pozzolanic additions such as fly ash and/or blast furnace slag,
together with nano-SiO2.
However there are two important problems to be considered
related to the use of nano-SiO2 in powder. The first refers to the
particles dispersion at the mixing stage of the mortars or concrete
and the second to the loss of workability due essentially to the high
specific surface of the particles. It is stressed that in the works
referred to in the previous paragraphs mechanical dispersion
techniques or ultra-sounds were used and in some cases the
authors refer the application of systems of treatment of the particles surface. An inadequate dispersion may cause a least favorable
of the compressive strength [8], among other effects.
When considering the use of binary mixes of fly ash and
nano-SiO2, the individual benefits of each of them can certainly
contribute to offset the problems of the other: reactive nano-SiO2
can improve the mechanical properties in the early ages (unlike
fly ash) while fly ash can improve the workability (contrarily to
nano-SiO2). As for the dispersion problem of the nano-SiO2 powder
particles, it is possible to replace them by water-based mixtures of
colloidal nano-SiO2.
With the evolution of the study of nano materials applied on
construction materials, nano titanium (nano-TiO2) has been widely
studied in various fields including the elimination of residual
waters and exhaustion gases and the improvement of the mechanical and durability properties of concrete [4]. Nazari and Riahi [1]
studied the influence of various nano materials on the mechanical
performance and microstructure of concrete. These authors refer
an increase of density of concrete with a significant improvement
both at the mechanical and durability level as the content of
nano-TiO2 in the mix increases. They justify these trends with an
acceleration of the formation of calcium-silicate-hydrate gel
(CSH) due to greater volume of calcium hydroxide (Ca(OH)2)
crystals especially in the first ages. Li et al. [2] and Zhang et al.
[9] demonstrate that the use of nano-SiO2 and nano-TiO2 causes
a significant improvement of the refinement if concretes porous
structure, increasing its resistance to chlorides penetration.
Fujishima et al. [8] also studied the influence of the use of nano
particles on the mechanical strength of concrete and obtained
similar results to those of Li et al. [2] and Zhang et al. [9]. The
excellent photo-catalytic properties of nano-TiO2 must also be
highlighted: when incorporated in concrete production, they can
contribute to the decomposition process of pollutant gases in
the atmosphere, simultaneously improving the performance of
concrete.

2. Literature review
Jawahar et al. [11] investigated the use of the mini slump cone
test to optimize the super plasticiser (SP) and viscosity modifying
agent (VMA) contents in SCMs. The SCMs mixes had 35% replacement of cement with class F FA and two different water/cement
(W/C) ratios by weight: 0.32 and 0.36. It is observed that, for the
same cementitious proportions, the optimum SP content was the
same for the mixes with 0.32 and 0.36 W/C. Mortar mixes with
0.36 W/C showed an increase in the rate of flow, i.e. lower viscosity
at each level of SP content than that of mixes with 0.32 W/C. It is
also observed that a minimum VMA content was required in the
mortar mixes with 0.36 W/C in order to stop bleeding, whereas
no VMA was required in the mortar mixes with 0.32 W/C as no
bleeding was observed at the optimum SP content. In practical
terms, it was seen that the mini slump cone test is the best choice
for SCM tests to evaluate the mortar spread and its viscosity (T20).
Also, it was seen that the sand content in mortar does not affect the

509

optimum SP content (saturation point) when the cementitious

proportions remain constant.
Nepomuceno and Oliveira [13] reported an experimental study
on the mortar phase for SCC. A series of SCMs were produced with
similar flow properties, measured by spread and mini V-funnel
tests, adequate to produce SCC. The water content and the modified carboxylic SP content were determined experimentally for
each mortar. Different contents of cement replacement materials
were used in binary blends, each one combining one of the two
types of cement with one of the three mineral additions selected:
limestone filer (LF), granite filler (GF) and FA. Each of the binary
blends of powders was combined in five proportions in volume
with the fine aggregate (VP/Vs). Mortars were tested for compressive strength at 28 days and this value was related to the water/
cement ratio, the percentage of cement replacement materials,
and the VP/Vs parameter. The analysis revealed the possibility of
establishing adequate mortar parameters to obtain simultaneously
self-compatibility and the required compressive strength of selfcompacting concrete.
Porro et al. [14] mentioned that the use of Nano-SiO2 particles
increases the compression strength of cement pastes. They also
stated that this phenomenon is not due to the pozzolanic reaction,
because calcium hydroxide consumption was very low but,
instead, to the increase of silica compounds that, in turn,
contribute to a denser microstructure.
Hui et al. [15] studied the mechanical properties of nano-Fe2O3
and nano-SiO2 cement mortars were experimentally studied. The
experimental results showed that the compressive and flexural
strengths at 7 and 28 days of the cement mortars mixed with
the nano-particles were higher than those of a plain cement
mortar. Therefore, it is feasible to add nano-particles to
improve the mechanical properties of concrete. The SEM study of
the microstructures between the cement mortar mixed with the
nano-particles and the plain cement mortar showed that the
nano-Fe2O3 and nano-SiO2 filled up the pores and reduced the Ca
(OH)2 compound between the hydrates. These mechanisms
explained the supreme mechanical performance of the cement
mortars with nano-particles.
Arefi et al. [16] did research on the compressive, tensile and
flexural strength of cement mortar containing Al2O3 nanoparticles
at 1%, 3% and 5% by weight of cement. The results show that the
mechanical properties of samples containing 1% and 3% Al2O3
nanoparticles are better than those of the ordinary cement mortar.
But, by increasing Al2O3 nanoparticles to 5%, the mechanical properties decreased severely. A SEM study of the microstructure of
cement mortar containing nanoparticles and ordinary cement
mortar showed that Al2O3 nanoparticles reduced the CaOH2 crystals, filled the pores and increased the density of cement mortar.
Oltulu and Sahin [17] studied the addition of both nano-SiO2,
nano-Al2O3 and nano-Fe2O3 powders and their binary and ternary
combinations on the compressive strength and capillary water
absorption of cement mortars containing FA. The powder content
used corresponded to 0.5%, 1.25% and 2.5% of the binder for all
mixes. The authors concluded that the addition of any single type
of oxide powders at 1.25% increased the compressive strength of
the mortars more efficiently than the other proportions. The use
of NS + NA powders at 1.25% maximized the compressive strength
relative to the control specimen. For all binary powder combinations, the rate of increase in strength reached generally their peak
at 28 days and gradually decreased through aging. Of all the
groups, the best results were obtained in the mortars added with
NS + NA + NF powders at 1.25%. For this specific mortar, 732%
increase in compressive strength and 14% decrease in capillary
absorption occurred relative to the control specimen.
Meng et al. [18] studied the effect of nano-TiO2 on the mechanical properties of cement mortar. The test results indicated that

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S. Rao et al. / Construction and Building Materials 96 (2015) 508517

when cement was replaced with nano-TiO2, the strength of the

cement mortar at early ages increased a lot and the fluidity and
strength at later ages decreased significantly. It seems that the
main reason for the improvement of strength is the decrease and
modification of the orientation index for the nucleus function,
rather than the increasing amount of hydration products. They also
concluded that, by adding superplasticizer and slag powder to the
cement mortar, the fluidity and strength at older ages of the
cement mortar with nano-TiO2 changed.
Nazari et al. [19] investigated the compressive strength and
workability of concrete by partial replacement of cement with
nano-phase TiO2 particles. TiO2 nanoparticles with an average
diameter of 15 nm were used with contents of 0.5%, 0.1%, 1.5%
and 2.0% by cement weight. They concluded that the use of
nano-TiO2 particles up to a maximum replacement level of 2.0%
produces concrete with improved strength. However, the maximum strength of concrete was gained at 1.0% of cement replacement. The workability of fresh concrete decreased when the
content of TiO2 nanoparticles increased. They also concluded that
partial replacement of cement with nano-phase TiO2 particles
improves the compressive strength of concrete but decreases its
workability.

3. Experimental programme
The main objective of this work is to study the strength and durability
properties of self-compacting mortars (SCMs) with incorporation of nano silica
(nano-SiO2) and nano titanium (nano-TiO2) in 1:1 and 1:2 mixes (ratio binder:sand
of 1:1 and 1:2). For this purpose, 4  4  16 cm specimens were cast with various
contents of nano-SiO2 (colloidal state) and nano-TiO2 (amorphous state) for
compressive and flexural testing of 1:1 and 1:2 SCMs. Specimens with 100 mm
diameter and 300 mm length were cast to test durability properties like porosity,
water absorption and carbonation.

3.1. Materials
The following materials were used: cement complying with NP EN 197-1 [20]
(cement type I-42.5 R with specific gravity of 3.14), whose chemical composition
and grading are provided in Tables 1 and 2; a mineral addition fly ash (FA)
complying with NP EN 450-1 [21] and NP EN 450-2 [22] with specific gravity of
2.30, whose chemical composition and grading are provided in Tables 1 and 2;
two siliceous sands complying with NP EN 12620 [23], one coarse (0/4) with specific gravity of 2.55, fineness modulus of 3.70 and water absorption of 1.10% and one
fine (0/1) with specific gravity of 2.58, fineness modulus of 2.03 and water absorption of 0.70%; a third-generation high-performance water-reducing admixture (SP)
complying with NP EN 934-1 [24] and NP EN 934-2 [25] (a modified polycarboxylic
high-range water-reducing admixture in liquid form with a density of 1.07); tap
water complying with NP EN 1008 [26].
In this study, two types of nano materials, nano-SiO2 (colloidal state) and
nano-TiO2 (amorphous), with various contents were used. The specific surface area
of nano-SiO2 is 260 m2/g and that of nano-TiO2 is 50 m2/g. The average particle size
of both nano materials is 20 nm. The pH of the nano-SiO2 solutions is between 9.4
and 10.4 whereas for nano-TiO2 it is 3.44.5.
Table 1
Chemical composition of the raw materials.

Chemical composition of raw materials (%)*

CEM I

FA

Al2O3
CaCO3
CaO (free)
CaO (total)
Cl
Fe2O3
K2O
MgO
Na2O
SiO2
SO3
TiO2
Insoluble residue
Loss of ignition

5.24

0.81
62.71
0.01
3.17

2.23

19.59
3.13

1.37
2.94

24.70

0.30
2.63
<0.01
5.40
1.11
1.01
0.89
54.70
1.38

5.10

These data are indicative values provided by the manufacturers.

Table 2
Grading of the raw materials.
Particle size, in microns*

1000
100
10
1
0.1
*

Passing %
CEM I

FA

100
98
38
5
0

100
96
45
2
0

These data are indicative values provided by the manufacturers.

3.2. Mix proportions

In this work two self-compacting mortars were selected (ratio binder:sand 1:1
and 1:2). As seen in Table 3, to each of these mortars nano-TiO2 in amorphous state
was added at 0.50%, 0.75% and 1.00% of cement mass (NTA, NTB and NTC respectively). Similarly nano-SiO2 in colloidal state (30% of nano silica) was added at
0.75%, 1.50% e 3.00% of cement mass (NSP, NSQ and NSR respectively). In the second
group of mortars it was necessary to compensate the apparent mixing water
content due to the colloidal state of the addition. All the SCM mixes had the same
effective W/C ratio and 30% of replacement of cement with fly ash.

3.3. Mortar mixture procedure

As found out by various authors [13,2731], the mixing procedure has a significant influence on the self-compacting mortars fresh-state properties, namely on
the optimization of the use of superplasticizers. They confirmed that the mixing
time until the superplasticizer is added is not irrelevant to its efficiency and consequently it alters the self-compatibility conditions of these mortars.
Based on the analysis of the proposals of these authors and bearing in mind the
experience collected so far, the mixing procedure adopted by Domone [27] and Jin
and Domone [28] was selected, very similar to the one used by Nepomuceno [13]
and Liu [29].
The complete mixing sequence takes 10 min and starts with the insertion of the
fine aggregates (sands) and fine materials and their mixing for approximately
1 min. The first water fraction, corresponding to 80% of the whole mixing water,
is then slowly added, without interrupting the mixing process for a further 1 min,
in order to optimize the homogenization. The second water fraction (the remaining
20%), mixed with the superplasticizer, is also slowly added without interrupting
the mixing process. The mixing proceeds at it normal speed for another 5 min.
The mixer is then switched off and the mix rests for 2 min. If necessary, this phase
can be used to clean the mixers paddle. Before starting the fresh-state tests, the mix
restarts for 1 min, always at the normal speed.

3.4. Test methods and sample preparation

3.4.1. Mini-cone slump-flow test for SCM
The determination of the slump-flow average diameter through the mini
slump-flow test using a conical mould allows determining the Gm parameter.
Given that there are still no normative references for this test, the choice was to
follow the test procedures used by Nepomuceno and Oliveira [13], based in turn
on Okamura et al. [32]:


Gm

Dm
D0

2
1

where Gm = relative slump-flow area; Dm = slump-flow average diameter, in mm;

D0 = initial diameter in the cones base, in mm.
The admissible range established by Nepomuceno and Oliveira [13] for the
value of Gm, considering what best suits the accomplishment of SCC, is 5.35.9.
As per EPG guidelines [33], all the SCM mixes have slump flow of 240 mm to
260 mm.

3.4.2. Mini V-funnel test for SCM

The determination of the flow time using the mini V-funnel test allows calculating the Rm parameter. Since there are still no normative references for this test, the
choice was to follow the test procedures used by Nepomuceno and Oliveira [13],
based in turn on Okamura et al. [32].
The result of this test is presented directly by the flow time (t), measured in
seconds:

Rm

10
t

where Rm = relative flow velocity, in s1; t = flow time, in s.

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S. Rao et al. / Construction and Building Materials 96 (2015) 508517

Table 3
Mix proportions of all mortars.
Mix proportions

*
**

CEM I

Fly ash

Sand0/1

Sand0/4

Water

W/C

SP*

Binder/sand**

1:1

Weight (kg/m )
Volume (m3)

665
0.212

286
0.124

485
0.190

485
0.190

286
0.286

0.43

5.0
0.0045

1.0

1:2

Weight (kg/m3)
Volume (m3)

490
0.156

210
0.091

695
0.273

695
0.273

211
0.211

0.43

7.35
0.0067

0.50

Paste volume
0.622
0.458

SP (% mass cement): mix1:1 = 0.75 and mix1:2 = 1.50.

Ratio binder: sand of 1:1 and 1:2.

The admissible range established by Nepomuceno and Oliveira [13] the value of
Rm, considering what best suits the compliance with SCC characteristics, is
1.141.30. As per EPG guidelines [33], all the SCM mixes have mini V-Funnel time
of 711 s.
3.4.3. Compressive and flexural strength test
The compressive and flexural strength tests were performed according to the
procedures described in NP EN 1015-11 [34], at 7, 28 and 91 days, in three
160  40  40 mm prismatic specimens. They were initially tested for flexural
strength, which resulted in two halves that were then tested for compressive
strength.
3.4.4. Immersion water absorption
The water absorption (total volume of penetrable pores) was determined
according to the procedure described in LNEC E 394 [35], in three 100 mm cubic
moulds, at 28 and 91 days. Three mass values were obtained: apparent mass of
saturated samples after immersion to constant weight (i.e. until the incremental
increase in mass was less than 0.1%), mass in the air while they were still saturated,
and mass of dry samples (oven dried at 105 5 C to constant weight, i.e. until the
increase in mass was less than 0.5%).
3.4.5. Carbonation resistance
Specification LNEC-E391 [37] and recommendation RILEM CPC-18 [38] were
used to determine carbonation resistance. A 100 mm diameter and approximately
50 mm thick sample of each SCC mix was tested after 14, 28, 56 and 91 days of
exposure in the CO2 chamber. All the specimens tested were subjected to wet
curing by immersion in water at 20 2 C until 14 days prior to the start of the test,
i.e. placing in the carbonation chamber. At that time, the specimens were sectioned
and their tops protected with an insulating coating. Then, the specimens were conditioned at 20 2 C and 50% RH until they were placed in the carbonation chamber
(28 days). The chamber had 5 1% of CO2, at 60 5% RH and 23 3 C. After the
required time of exposure to these conditions the specimens were removed from
the chamber, broken into four pieces and the carbonation depth was measured
using a colorimetric method (with phenolphthalein at 0.1%).

4. Tests results and discussion

4.1. Fresh-state properties
The fresh-state performance of self-compacting mortars
depends on many factors, the most relevant of which were
mentioned in Section 1. However, it is stressed that the objective
in terms of spread and mini V-funnel test results was simply to
comply with the workability parameters defined in the reference
documents [13,2731], in order to reach self-compatibility, which
was successfully done for all the mixes produced.
Table 4 and Fig. 1 present a summary of the fresh-state results
for all the mixes studied. As expected, there is a decrease of spread
and flowability with the addition of both nano-TiO2 and nano-SiO2
for both mortar families (ratios 1:1 and 1:2).
The flowability evaluated by the mini V-funnel shows a minor
scatter in the 1:1 family mixes (independently of the nano material
used). As for the 1:2 family mixes, there is a minor scatter with the
Rm values always between 0.77 s1 e 0.89 s1. However, the spread
losses of the 1:2 mixes is almost nil independently of the nano
material used by comparison with the reference mortar, contrarily
to the 1:1 mixes.
The results presented, relating to the mixes with nano-SiO2, can
be confirmed by the work of Senff et al. [36,44]. These authors

Table 4
Mini-cone slump-flow and mini V-funnel test results.
Mix

1:1
NT1A (0.5%NT)
NT1B (0.75%NT)
NT1C (1.00%NT)
NS1P (0.75%NS)
NS1Q (1.50%NS)
NS1R (3.00%NS)
1:2
NT2A (0.5%NT)
NT2B (0.75%NT)
NT2C (1.00%NT)
NS2P (0.75%NS)
NS2Q (1.50%NS)
NS2R (3.00%NS)

Mini-cone slump-flow

Mini-V-funnel

Dm (mm)

Gm

t (s)

Rm (s1)

310.0
283.0
275.0
260.0
284.0
282.5
265.0
300.0
297.5
292.5
290.0
297.5
292.5
285.0

8.6
7.0
6.6
5.8
7.07
7.0
6.0
8.0
7.9
7.6
7.4
7.9
7.6
7.0

7.4
7.8
7.9
9.7
7.6
9.0
9.9
10.4
11.2
12.0
12.7
12.6
12.8
13.0

1.35
1.28
1.27
1.03
1.32
1.11
1.01
0.96
0.89
0.83
0.79
0.79
0.78
0.77

NS = nano-SiO2; NT = nano-TiO2.

studied the effect of nano-SiO2 on the fresh-state behavior of

cementitious mortars and mention unequivocally that, as the
nano-SiO2 content progressively increases (0%, 1.0%, 1.5%, 2.0%
and 2.5% in cement weight), the yield stress after 75 min is
126.4%, 4.3%, 14.7%, +38.1% and +66.5% (relative to the maximum test time 150 min for the 2.5% nano-silica containing
sample), respectively.
According to Sections 1 and 2, and as occurred in both our work
and that of various authors [36,39,43,44], it is possible to state that
the use of additions with a specific surface higher than that of the
cement particles (as is the case of nano-SiO2), implies a higher consumption both of water and of superplasticizer to maintain the
same level of workability of an equivalent mix without the use of
this nano-material.
Regarding the use of the nano-TiO2, it is possible to compare the
results of our work with those of Senff et al. [44]. These authors
mention a significant increase of the torque values and yield stress
with the addition of nano-TiO2 with a corresponding decrease of
the open testing time.
Generally it can be stated that the influence of both nano-SiO2
and nano-TiO2 on the fresh-state performance of the mortars is
more significant for the 1:1 family in terms of flow. In the remaining cases, the workability losses are minimal and perfectly within
the reference values.
4.2. Compressive and flexural strength test
The results of the uniaxial compressive and flexural tests for all
mixes produced are presented in Table 5 and Figs. 24.
These elements show a clearer growth of the early-age (7 days)
compressive strength of the mixes with nano-SiO2 (in both the 1:1
and 1:2 families). As for the mixes with nano-TiO2 (in both the 1:1
and 1:2 families), they show a more monotonic evolution of the
compressive strength beyond the early ages. For older ages it is
found that all mixes reach compressive strength values higher than

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S. Rao et al. / Construction and Building Materials 96 (2015) 508517

12

2.0

11

1.8
1.6

1.2
1.0
0.8

NS2R (3.00%NS)

NS2P (0.75%NS)

NS2Q (1.50%NS)

1:1

NS2R (3.00%NS)

NS2P (0.75%NS)

NS2Q (1.50%NS)

NT2C (1.00%NT)

NT2B (0.75%NT)

1:2

NT2A (0.50%NT)

NS1R (3.00%NS)

NS1P (0.75%NS)

0.2

NS1Q (1.50%NS)

2
NT1C (1.00%NT)

0.4

NT1B (0.75%NT)

1:1

min

0.6

NT2C (1.00%NT)

mx

NS

NT

NT2B (0.75%NT)

Ref

NS

1:2

min

NT

NT2A (0.50%NT)

Ref

NS1R (3.00%NS)

1.4

NS1P (0.75%NS)

NS1Q (1.50%NS)

mx

NS

NT

NT1C (1.00%NT)

Ref

NS

NT1B (0.75%NT)

NT

NT1A (0.50%NT)

Ref

Mini-V-funnel (Rm S-1)

NT1A (0.50%NT)

Mini-cone slump-flow (Gm)

10

Fig. 1. Mini-cone slump-flow (left) and mini V-funnel (right) test results.

Table 5
Compressive, flexural strength and water absorption test results.
Mix

Compressive strength (MPa)

1:1
NT1A (0.5%NT)
NT1B (0.75%NT)
NT1C (1.00%NT)
NS1P (0.75%NS)
NS1Q (1.50%NS)
NS1R (3.00%NS)
1:2
NT2A (0.5%NT)
NT2B (0.75%NT)
NT2C (1.00%NT)
NS2P (0.75%NS)
NS2Q (1.50%NS)
NS2R (3.00%NS)

Hardening coefficients (compressive

strength)

Flexural strength (MPa)

Porosity (%)

7 days

28 days

91 days

7 days

28 days

91 days

7 days

28 days

91 days

28 days

75.5
75.3
66.9
54.5
73.2
71.6
70
74.2
73.4
69.3
62.2
73.6
71.9
70.3

91.4
87
84.2
83.1
88.4
86.3
84.2
94.9
92
87.8
76.6
90.4
86.3
83.3

106.3
108.1
99
88.1
96.7
94.7
94.2
101.6
104.1
98.8
92.7
98.9
95.4
92

0.83
0.82
0.73
0.60
0.80
0.78
0.77
0.81
0.80
0.76
0.68
0.81
0.79
0.77

1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00

1.16
1.18
1.08
0.96
1.06
1.04
1.03
1.11
1.14
1.08
1.01
1.08
1.04
1.01

10.5
8.2
6.9
7
13.8
11.8
8.4
8.8
11.1
12.4
10.2
12
12.2
11

10.7
13.1
12.9
13
13.4
12.5
12
12.9
11.8
13.6
12.1
13.5
13
11.5

14.2
14.9
13.4
13.1
14.8
13.7
12.8
13.5
13.7
11.8
9.9
14.5
14.2
13.8

6.2
6.4
6.4
6.5
7.1
7.2
7.6
4.1
5.5
5.8
5.9
6.5
6.7
6.9

NS = nano-SiO2; NT = nano-TiO2.

Fig. 2. 7-, 28- and 91-day compressive strength of all mixes.

90 MPa (except for the NT1C mix), with very similar values for the
equivalent mixes with each of the nano materials.
These differences may be seen both in the graphs of mechanical
strength versus age (Fig. 3) and in those of mechanical strength versus
replacement ratio (Fig. 4). In terms of absolute values, for both
families studied and as expected, the compressive strength increases
with age and decreases with the nano materials addition ratio.
The hardening coefficients presented in Table 5 confirm what
was referred in the beginning of this section, i.e. the 7-day compressive strength of the 1.00% mixes of nano-TiO2 is generally
lower than that of the remaining mixes. With the exception of
the NT1C and NT2C mixes, they all showed values higher than
70% of those at 28 days (independently of the nano material used).
None of the 7-day strength values is higher than 83% of the corresponding values at 28 days. At older ages the compressive strength
tends to stabilize, increasing at the most 18% relative to the 28-day
value (NT1A mix) and 14% for the NT2A mix. Increasing the addition of both nano-SiO2 and nano-TiO2 generally decreases the
hardening coefficient, by less than 10% in most mixes.
According to Table 5, the scatter of the flexural strength results
is lower than of the compressive strength results. There is also a
less significant increase of the results with the addition of both
nano-TiO2 and nano-SiO2. For older ages (91 days) the flexural

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S. Rao et al. / Construction and Building Materials 96 (2015) 508517

100

100

90

80

70

1:1
NT1A (0.50%NT)
NT1B (0.75%NT)
NT1C (1.00%NT)

60

Compressive strength (MPa)

110

Compressive strength (MPa)

110

90

80

70

1:2
NT2A (0.50%NT)
NT2B (0.75%NT)
NT2C (1.00%NT)

60

50

50
0

14

28

42

56

70

84

98

14

28

Age (days)

100

90

80

1:1
NS1P (0.75%NS)
NS1Q (1.50%NS)
NS1R (3.00%NS)

Compressive strength (MPa)

100

Compressive strength (MPa)

110

60

56

70

84

98

Age (days)

110

70

42

90

80

70

1:2
NS2P (0.75%NS)
NS2Q (1.50%NS)
NS2R (3.00%NS)

60

50

50
0

14

28

42

56

70

84

98

14

28

42

56

70

84

98

Age (days)

Age (days)
Fig. 3. Compressive strength versus age for all mixes.

strength of the 1:2 mixes with 3% of nano-SiO2 increases approximately 4% (relative to the reference mix) while for the 1:1 mixes
this increase is almost 20%.
Compared to the results obtained by other studies regarding the
mechanical behavior of the type of mixes studied (with nano-SiO2
and nano-TiO2), there is some contradictory data. Some authors
[36,44,45] mention a practically nil variation of the mechanical
strength with the addition both of nano-TiO2 and nano-SiO2 when
compared to the reference mixes (without nano-materials). As
observed in our work, the lower mechanical strength (mainly in
more advanced ages) with the addition of the nano-materials
under study, when compared to the reference mixes, is usually
attributed to the difficult dispersion of the nano-particles in the
mixes of both mortars and concrete [36,4446]. Li [47] mentions
that, regarding concrete mixes with fly ash and nano-SiO2, the high
contents of calcium hydroxide (produced in the early stage of the
hydration process) can be consumed by the nano-SiO2, resulting
in a lower available quantity of that compound for the pozzolanic
reactions with fly ash at more advanced ages, causing a decrease of
the mechanical strength of these mixes mainly at those ages.
On the other hand, some authors [4850] present results with a
significant increase of the mechanical strength due to the addition
of the nano-materials under study. Shih et al. [48] show gains of
2025% of the compressive strength of mortars with nano-SiO2 relative to the reference mixes (without additions). These authors
[4850] generically mention that the improvement observed in
the mechanical strength, due to the incorporation of nano-SiO2,
is essentially caused by an increase of the pozzolanic activity,
resulting in a higher quantity of calcium silicate hydrate and a denser microstructure, i.e. a microstructure with greater compacity
[51].

4.3. Immersion water absorption

The results of the water absorption by immersion test of all the
mixes produced are presented in Table 5. These results are also
presented graphically in Fig. 5.
This test, performed according to the procedure presented in
Section 3.4.4, essentially evaluates the porosity of concrete.
However, the test has some limitations, namely that it measures
the volume of accessible pores only, usually called open porosity,
i.e. this value does not represent the absolute porosity of the material since it does not consider the volume of closed pores.
From Table 5 and Fig. 5 it is found that the water absorption by
immersion significantly increases when the nano materials content
increases. It is also found that there is a decrease of the absorption
from the 1:1 family mixes to the 1:2 family mixes, and consequently with the decrease of the volume paste in the 1:2 mixes.
These variations can be confirmed in the reference mixes: 6.2%
for the 1:1 mix and 4.1% for the 1:2 mix. However it is stressed that
the 1:2 family mixes have a higher change (from the reference
value) than the 1:1 family mixes. It can be further seen that the
mixes with nano-SiO2 present water absorption by immersion values slightly higher than those with nano-TiO2 independently of the
mortars family (1:1 or 1:2).
It can be generally stated that the open porosity determined by
the water absorption by immersion test (Table 5 and Fig. 5) presents values in agreement with those of other authors in equivalent mixes [1,4,5]. The porosity values are lower for a 0.5%
addition of nano-TiO2 and they are maximum in the mixes with
nano-SiO2 independently of its ratio of incorporation. Regarding
the microstructure of the mixes with nano-particles (namely with
nano-SiO2), Li et al. [49] mention that the difficulty in dispersing

110

110

100

100

Compressive strength (MPa)

NT2 (mix 1:2)

NT1 (mix 1:1)

S. Rao et al. / Construction and Building Materials 96 (2015) 508517

Compressive strength (MPa)

514

90

80

70

60

NT1 (mix 1:1)

7 days
28 days
91 days

90

80

70

60

NT2 (mix 1:2)

7 days
28 days
91 days

50

50
0.00%

0.50%

0.75%

0.00%

1.00%

0.50%

110

110

100

100

90

80

70

60

0.75%

1.00%

NT (%)

Compressive strength (MPa)

NS2 (mix 1:2)

Compressive strength (MPa)

NS1 (mix 1:1)

NT (%)

NS1 (mix 1:1)

7 days
28 days
91 days

90

80

70

60

NS2 (mix 1:2)

7 days
28 days
91 days

50

50
0.00%

0.75%

1.50%

3.00%

0.00%

0.75%

1.50%

3.00%

NS (%)

NS (%)
Fig. 4. Compressive strength versus NT and NS%.

8.0

28 days

7.6

Water absorption m (%)

7.5

7.1 7.2
6.9

7.0

6.7
6.4 6.4 6.5

6.5

6.5

6.2
5.8 5.9

6.0

5.5

5.5
5.0
4.5

4.1
NS2R (3.00%NS)

NS2P (0.75%NS)

NS2Q (1.50%NS)

NT2C (1.00%NT)

NT2B (0.75%NT)

1:2

NT2A (0.50%NT)

NS1R (3.00%NS)

NS1P (0.75%NS)

NS1Q (1.50%NS)

NT1C (1.00%NT)

NT1B (0.75%NT)

NT1A (0.50%NT)

1:1

4.0

Fig. 5. 28-Day water absorption by immersion of all mixes.

these materials can have as main consequence the appearance of

weaker areas, in the form of voids that can cause the formation
of a less dense and homogeneous microstructure and, as observed
in Section 4.2, a reduction of the mechanical strength.
4.4. Carbonation resistance
The carbonation depth results of all mixes are presented in
Table 6. For each of the test ages, the average carbonation depth
(dkmxd) is provided. In the table the result <1 of the carbonation
depth means that no measurable carbonation was detected at

any of the ages analyzed and consequently the corresponding coefficient is assigned the minimum value of 1 mm/year0.5. Fig. 6 presents the carbonation depth in function of the test age (graphs on
the left) and of the square root of time (graphs on the right), from
which the carbonation coefficients line (also in Table 6) were
determined, corresponding to the slope of the linear regression.
Fig. 6 shows the variation of the carbonation depth with time
(graphs on the left) and the same depth in function of the square
root of time (graphs on the right), from which the respective carbonations coefficients were determined, corresponding to the
slope of the regression line (and presented in Table 6).
A preliminary evaluation of the carbonation depth results in
Table 6 shows that the 1:1 family mortars with nano-TiO2 and
the mix with 0.75% of nano-SiO2 did not show any carbonation
effect up to 91 days of exposure in the accelerated carbonation
chamber. The same occurred in 1:2 family mortars with 0.5% of
nano-TiO2, i.e. these mixes proved to be practically impermeable
to carbonation in the time period studied. The remaining mixes
had a very similar behavior with carbonation depths always lower
than 10 mm, with the exception of the 1:2 mix with an addition of
3% of nano-SiO2 that showed after 28 days of exposure depths of
15 mm, reaching 20 mm at 91 days (maximum exposure time in
this study). The mixes with nano-TiO2 generally showed lower carbonation depths than those of the mixes with nano-SiO2. Similarly
the 1:1 family mortars showed lower carbonation depths than
those of the 1:2 family mortars.
Concrete carbonation may be quantified by the corresponding
coefficient, through the variation of the carbonation depth over
p
time, using equation x = k t (x = kt(1/n) with n = 2). The analysis
of the graphs on the right in Fig. 6 shows that the equation indeed
applies, with reasonable correlation coefficients always above 0.9,
with the exception of mix NS2P with R2 = 0.892. However, according to Neville [39] or Bertolini et al. [40], among others, this equation involving the square root of time cannot be applied to non-

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S. Rao et al. / Construction and Building Materials 96 (2015) 508517

Table 6
Depth of carbonation (mm) and corresponding coefficients of all mixes.
Mix

dkm14d

dkm28d

dkm56d

dkm91d

Kc (mm/year0.5)

R2

1:1
NT1A (0.5%NT)
NT1B (0.75%NT)
NT1C (1.00%NT)
NS1P (0.75%NS)
NS1Q (1.50%NS)
NS1R (3.00%NS)
1:2
NT2A (0.5%NT)
NT2B (0.75%NT)
NT2C (1.00%NT)
NS2P (0.75%NS)
NS2Q (1.50%NS)
NS2R (3.00%NS)

<1
<1
<1
<1
<1
3
4
<1
<1
2
3
2
3
5

<1
<1
<1
<1
<1
4
5
<1
<1
4
4
3
4
15

<1
<1
<1
<1
<1
5
9
<1
<1
6
5
6
7
16

<1
<1
<1
<1
<1
6
10
<1
<1
8
6
8
8
20

1
1
1
1
1
11.94
20.92
1
1
16.39
11.94
41.93
19.78
16.36

0.973
0.971

0.989
0.990
0.892
0.960
0.941

Fig. 6. Depth of carbonation versus age and

t for all mixes.

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S. Rao et al. / Construction and Building Materials 96 (2015) 508517

stationary exposure conditions, i.e. natural exposure situations in

which the material is subjected to humidity and temperature variations and CO2 concentration levels significantly lower than those
of the accelerated test. Bertolini et al. [40] refer that for cementbased materials under natural exposure conditions the reduction
of the carbonation process over time is steeper than that described
by the parabolic equation x = kt(1/n) and that in these cases the n
value tends to be higher than 2. As seen in our work, Bertolini et al.
[40] argue that in cement-based materials with high compacity the
carbonation process tends to be negligible. Confirming other
authors, namely Neville [39], Bertolini et al. [40], Silva and de
Brito [41,42], in the more compact mixes of this work carbonation
was negligible even after exposure times up to a quarter of a year.
Despite the problems associated with the dispersion of this type
of particles [1,4,5,36,4447,49], numerous authors [4549] mention the advantages, in terms of compacity of the mixes, mainly
with nano-SiO2. In that sense, Li et al. [49] mention how the
nano-SiO2 can participate in the hydration process, at least as a
nucleation point, but mainly generating calcium silicate hydrate
through the reaction with calcium hydroxide and consequently
causing a higher compacity of the microstructure. This has
unequivocal advantages in terms of resistance to the progression
of the main degradation mechanisms (namely CO2 penetration),
even when small quantities of nano-SiO2 are not well dispersed.

5. Conclusions
All self-compacting mortars produced with and without nano
materials (SiO2 and TiO2) complied with the reference values
intended concerning the fresh-state properties, namely those
referring to the mini-cone and the mini V-funnel. Despite the differences observed between reference and nano-materials mixes,
it is possible to state that all mixes are self-compacting and there
are no significant changes to the fresh-state properties with the
addition of these nano materials. This is equally true in the 1:1
family mixes and the 1:2 family mixes. It is however pointed out
that both nano-materials cause a decrease of the open testing time
that should be taken into account in the case of practical
applications.
Concerning the hardened-state properties, it is concluded that
the compressive strength growth rate decreased with the addition
of these nano materials in both the 1:1 and 1:2 mixes. The flexural
strength decreases with the addition of nano particles, especially
3.0% of SiO2 in the 1:1 family and 1.0% de TiO2 in the 1:2 family,
relative to the reference mortars (1:1 and 1:2). As observed by various authors, the negative influence in mechanical strength of the
difficulty of dispersion of the nano-particles under study in the
mix should be highlighted. Nevertheless, one should also stress
that the more significant losses of compressive strength (relative
to the reference mix, without nano-materials) were registered in
the mixes with nano-TiO2, with a maximum value at 91 days of
approximately 18% in the mix with 1% of nano-TiO2. The strength
losses regarding the mixes with nano-SiO2 are minimal (always
lower than 10% relative to the reference mixes without nanomaterials).
The water absorption by immersion (open porosity) increases
with the addition both of nano-SiO2 and nano-TiO2, relative to
the reference mortars (1:1 and 1:2). There is a slight decrease of
porosity in the 1:2 family mixes relative to the 1:1 family mixes.
The results allow stating that generally in the case of the 1:1
family mixes, the 1:2 reference mix and the NT2A mix, their
greater compacity creates an almost impenetrable barrier to CO2,
significantly retarding its propagation. These high compacity mortars are usually associated to a low water-accessible porosity,
which represents the main CO2 penetration path. As confirmed in

Section 4.3 by the water absorption by immersion results, these

mixes are the ones with the lowest accessible porosity values
and the lowest carbonation coefficients. Concerning the influence
of the additions on the degradation mechanism analyzed, the differences found between the nano materials used in terms of carbonation resistance, essentially in the 1:2 family mixes, are
highlighted: the mixes with nano-TiO2 show an improvement.
Acknowledgements
The authors acknowledge the support of Instituto Superior de
Engenharia de Lisboa (Polytechnic Institute of Lisbon) and Instituto
Superior Tcnico (University of Lisbon) through the Programa de
apoio formao avanada de docentes do Ensino Superior
Politcnico (PROTEC) for facilitating this work under the context
of the PhD scholarship with the reference SFRH/PROTEC/67426/
2010. The support of Foundation for Science and Technology
(FCT) and of the CERis-ICIST research centre is also acknowledged.
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