356 Int. J. Materials and Product Technology, Vol. 50, Nos.

3/4, 2015

Effect of nano ZnO2 and lime water curing on strength

and water absorption of concrete

Farshad Vazinram
Civil Engineering Department,
Abbaspour Faculty of Engineering,
Shahid Beheshti University,
Tehran, Iran
Email: f_vazinram@sbu.ac.ir

Mostafa Jalal*
Young Researchers and Elites Club,
Science and Research Branch,
Islamic Azad University,
Tehran, Iran
Fax: +98-21-73932418
Email: m.jalal.civil@gmail.com
*Corresponding author

Mohammad Yavari Foroushani

Young Researchers and Elite Club,
Khomeinishahr Branch, Islamic Azad University,
Khomeinishahr, Esfahan, Iran
Email: mohammad.yf2011@gmail.com

Abstract: Assessment of nano ZnO2 and lime water curing effects on

compressive strength and water absorption of concrete has been carried out in
this paper. Nanopowders of ZnO2 considered as a viable fraction of ordinary
Portland cement (OPC) in percent of 1, 2, 3 and 4 wt% were added into the
binder of concrete. Specimens cured in two media as ordinary water and
saturated lime water for 7, 28 and 90 days were analysed for compressive
strengths and water absorptions of concrete specimens, as representative
indices for mechanical and transport properties, respectively. The results
indicate that ZnO2 powders are able to improve significantly the concrete
compressive strength, and also reduce water absorption which could lead to
enhanced durability of concrete. Improved strength and water resistance was
noted when the specimens cured in saturated limewater related with those cured
in water. ZnO2 nanopowders can improve the filler effect, and the high
pozzolanic action of fine nanoparticles increases substantially the quantity of
strengthening gel leading to enhanced and water resistance of nano ZnO2
blended concrete.

Keywords: concrete; nano ZnO2; lime water; water absorption; compressive

strength.

Copyright © 2015 Inderscience Enterprises Ltd.

 Effect of nano ZnO2 and lime water curing on strength and water 357

Reference to this paper should be made as follows: Vazinram, F., Jalal, M. and
Foroushani, M.Y. (2015) ‘Effect of nano ZnO2 and lime water curing on
strength and water absorption of concrete’, Int. J. Materials and Product
Technology, Vol. 50, Nos. 3/4, pp.356–365.

Biographical notes: Farshad Vazinram is currently an Assistant Professor at

Shahid Beheshti University (SBU) and he is also the Head of the Civil end
Environmental Engineering Department.

Mostafa Jalal is currently a Research Assistant at Amirkabir University of

Technology and his research focus is on concrete and cement-based materials
at Concrete Technology and Durability Research Center. He is also a
distinguished member of Young Researchers and Elites Club.

Mohammad Yavari Foroushani has received his BS degree from

IAU-Najafabad Branch, and is currently a member of Young Researchers and
Elites Club.

1 Introduction

Nowadays, the micro-level does not provide enough insights into building materials.
Therefore, all around the world, increasing amounts of funding are being directed to
research projects dealing with material properties on the nano-level, which is claimed to
have a tremendous potential for the future (Scrivener and Kirkpatrick, 2008). The
fundamental processes that govern the properties of concrete are affected by the
performance of the material on nano-scale. The main hydration product of cement-based
materials, the C-S-H gel, is a nano-structured material (Sanchez and Sobolev, 2010;
Constantinides and Ulm, 2007; Richarson, 2000). The mechanical properties and the
durability of concrete mainly depend on the refinement of the microstructure of the
hardened cement paste and the improvement of the paste-aggregate interface zone (ITZ)
(Nili et al., 2010).
Compressive strength assessment of concrete is a main and probably the most
important mechanical property, which is usually measured after a standard curing time.
Concrete strength is influenced by lots of factors like concrete ingredients, age, ratio of
water to cementitious materials, etc. The pore structure determines the transport
properties of cement paste, such as permeability and ion migration. In the hydrated paste,
the capillary and gel pores can be distinguished. The gel pores are very small. Although
they constitute a network of open pores, the permeability of this network is very low.
Conversely, the capillary pores are relatively large spaces existing between the cement
grains. It is the capillary porosity that greatly affects the permeability of concrete
(Perraton et al., 1994).
Blended (or pozzolanic) cements are being used world-wide to produce dense and
impermeable concrete. They contain a blend of portland cement clinker and a variety of
natural pozzolans and/or supplementary cementing materials such as blast furnace slag,
fly ash, silica fume, etc. The use of these materials is also environment friendly because it
contributes to reduce the CO2 emission to the atmosphere (Malhotra, 1998). The
358 F. Vazinram et al.

beneficial effects of incorporating these materials in concrete are widely discussed in the
literature (Berke, 1989; Swamy, 1991; Hussain and Rasheeduzzafar, 1994; Ozyıldırım
and Halstead, 1994; Guneyisi et al., 1998).
There are several works on incorporating nanoparticles into concrete specimens to
achieve improved mechanical and durability properties most of which have focused
on using SiO2 nanoparticles and TiO2 nanoparticles (Jalal et al., 2012, 2013; Haji
Sotoudeh and Jalal, 2013). However, the other nanoparticles (such as ZnO2 nanoparticles
in this work) have rarely been investigated and some of researchers do not agree
that the other nanoparticles could be pozzolans. It seems that several works are needed to
introduce these new materials as cement replacement. Also to make a comparative
study on different nano-ceramics effects on properties of cement-based materials,
nano ZnO2 also seems to be useful to be included in the study as one of these
nano-ceramics.
Regarding environmental impacts of nano ZnO2, it can be said that nanotechnology as
any other kind of technology despite many advantages, may have some side effects.
However, since nanotechnology is rather new, as per authors’ knowledge, the long-term
and environmental impacts of nano materials used in concrete and cement-based
composites have not been reported. Still it could be beneficial as nanoparticles have been
used together with higher volumes of industrial wastes, such as fly ash and slag, to reduce
cement content and thereby reducing CO2 emission and energy consumption due to
cement production, which is of great importance from environmental point of view, as
discussed in the literature (Shi and Qian, 2000; Rosselló-Batle et al., 2010; Becchio et al.,
2009).
In the present work, nano ZnO2 and lime water curing effects on compressive strength
and water absorption of concrete have been investigated. Since strength assessments and
water permeability of concrete are joined together to affect the final performance of
concrete, considering compressive strengths together with water absorption of concrete
specimens seems essential. Hence, in this work, both water absorption and compressive
strength of concrete specimens have been assessed.

2 Materials and method

2.1 Materials
Concrete ingredients in the mix design are as follows:
The aggregates used were crushed lime stone that the grain size distribution of the
aggregates is given in Table 1. The fine aggregates used were crushed quarry sand with
particles ranging from 80 µm to 4.75 mm in size. Its bulk density, fineness modulus and
sand equivalent were 2.54 kg/m3, 2.78% and 70% respectively. The coarse aggregates
were natural crushed limestone, with maximum size of 4.75 mm and 19.1 mm with a
specific gravity of 2.57 kg/m3.
 Effect of nano ZnO2 and lime water curing on strength and water 359

Table 1 Grain size distribution of aggregates

Total
Sieve no. 1.1/2 1 3./4 1./2 3./8 4 8 16 30 50 100 200 Pan weight
(g)
Grain size 38.1 25.4 19.1 12.5 9.5 4.75 2.36 1.18 0.6 0.3 0.15 0.08 - -
(mm)
Remained 0 0 203 566 343 392 0 0 0 0 0 0 0.9 1,504
by weight
Passed (%) 100 100 93.3 74.5 63.1 49.1 34.2 22.6 13.3 8.68 1.11 0.15 0 -

Portland cement Type II with cement content of 350 kg/m3 was used which its properties
are given in Table 2. Nano ZnO2 with average particle size of 40 nm produced by Suzhou
Fuer Import & Export Trade Co., Ltd. was used as received. The properties of nano ZnO2
particles are shown in Table 3. Scanning electron microscopy (SEM) images of the
nanoparticles determined by HITACHI type S-3000N and X-ray diffraction (XRD)
spectrum of ZnO2 nanopowder prepared by Philips type PW-1730, are shown in
Figures 1 and 2 respectively.
Table 2 Chemical composition and physical properties of cement

Blaine
Chemical Loss of Specific
SiO2 Al2O3 Fe2O3 CaO MgO SO3 K2O Na2O fineness
analysis (%) ignition gravity
(cm2/g)
Cement 25.66 5.09 3.86 60.12 1.27 2.42 0.63 0.36 0.98 3.15 3260
composition

Table 3 Properties of nano ZnO2

Diameter (nm) Surface volume ratio (m2/g) Density (g/cm3) Purity (%)
40 ± 5 130 ± 15 < 0.13 > 99.9

Figure 1 XRD spectrum of ZnO2 nanoparticles (see online version for colours)
360 F. Vazinram et al.

Figure 2 SEM micrograph of ZnO2 nanoparticles

2.2 Specimens preparation and testing methodology

2.2.1 Preparation
Cubes of 100 mm edge for compressive strength tests were used. Tests were carried out
in triplicate specimens and average compressive strength values were considered.
The materials were mixed in dry condition for 2 min, and for another 3 min after
adding the water. Cubes of 100 mm edge for compressive strength tests were cast and
compacted in two layers on a vibrating table, where each layer was vibrated for 10 s. The
moulds were covered with polyethylene sheets and moistened for 24 h. Then, the
specimens were demoulded and cured in water (W) and saturated limewater (LW) at a
temperature of 20°C prior to test days.

2.2.2 Strength and water absorption determination

Compressive strengths of the concrete specimens were determined conforming

ASTM C39 (2001). Standard slump tests conforming to ASTM C143 (2001) were used to
determine the workability of the concrete. Setting time of the specimens was regulated
according to the ASTM C191 (2001) standard.
Water permeability tests are performed with several methods such as percentage
of water absorption, rate of water absorption and coefficient of water absorption.
In this work, the water permeability of the prepared and cured specimens of concretes
is expressed as percentage of water absorption, being considered as evaluation of the
pore volume which occupied by water in saturated state, or porosity of concrete after
water absorption. Water absorption values of ZnO2 nanoparticle blended concrete
samples were measured as per ASTM C642 (2001) standard after 7, 28 and 90 days of
moisture curing.
The designed samples are composed of CNx-W, or CNx-LW which consists of
concrete (C), nano (N) particles (x, %), and curing water (W) or lime water (LW),
respectively.
 Effect of nano ZnO2 and lime water curing on strength and water 361

3 Results and discussion

The compressive strength results of different mixtures of concrete samples are illustrated
in Figure 3. Comparison of results after 7, 28, and 90 days, tested samples show an
increasing compressive strength for ZnO2 up to 4% replacement (CN4-W, or CN4-LW).

Figure 3 Compressive strength of nano ZnO2 blended concrete cured in water and lime water at
different aging times (see online version for colours)

7 days 28 days 90 days

50
45
40
Compressive strength (MPa)

35
30
25
20
15
10
5
0
CN0-W CN1-W CN2-W CN3-W CN4-W CN0-LW CN1-LW CN2-LW CN3-LW CN4-LW

Sample ID

Compressive strength improvement of concrete containing nano ZnO2 could be explained

based on C-S-H gel formation as follows:
Alite (C3S) is the mineral component to be found in cement in the largest ratio (50%),
under the form of colourless and equisized grains (Neville, 2003). This is the calcium
silicate with the highest hydrolysis reaction which very easily reacts to water. C3S
hydration defines to a large extent the behaviour of the cement, though its rate is not
constant and not even the rate changes are constant. C3S rapidly hydrates and hardens the
cement slurry and enforces high initial (one to three days) and final mechanical strengths
(Jumate and Manea 2011).
Belite (C2S) is the mineral component that exhibits three or even four polymorphous
forms, easily reacts with water and turns into a hydrated dicalcium silicate. This slowly
hydrates and hardens the cement slurry and improves the cement mechanical strengths
after seven days. After 28 days, this mineral compound hardens and its mechanical
strength will be very close to that of the calcium silicate hydrate originating in C3S
(Jumate and Manea, 2011).
The hydration and hydrolysis reactions of the two mineral compounds above also
produce hydrosilicates that initially have a gel structure similar to that of the natural
mineral called tobermorite. The calcium silicate hydrates form the majority of the
hydration products, present a gel structure, where the solid phase is made up of a lattice
of microcrystals, initially of angstrom size with eyes filled with a saturated composition
of components: in a later stage, the crystals develop, age and strengthen, leading to the
increase of the mechanical strengths (Jumate and Manea, 2011; Serban, 1998; Molnar
et al., 2010).
362 F. Vazinram et al.

Tricalcium silicate (C3S) can be accelerated by addition of nanoscaled particles of

ZnO2. This process can be described by assuming that ZnO2 nanoparticles are spread in
the water between the cement particles and serve as seeds for the formation of C-S-H
phase. Thus the formation of the C-S-H phase is no longer limited on the grain surface
alone, as in the pure C3S, but also takes place in the pore space. The evasion of
time-consuming nucleation processes and the large number of seeds thereby cause an
acceleration of C3S hydration. At the same time the hardened paste should develop less
porosity when compared with pure C3S.
When nano ZnO2 is added to hydrating C3S, an early pozzolanic reaction on the
nanoparticles’ surface occurs that forms C-S-H seeds. These seeds then will act like the
pure C-S-H seeds described above. Due to the time that is necessary for nucleation
processes the acceleration is not as strong as for the addition of C-S-H particles, which
directly serve as nucleation seeds.
A faster formation of portlandite and faster consumption of C3S suggests that the
formation of C-S-H-phase is accelerated as well. Since the C-S-H-phase is the main
component for strength development in cement, this acceleration should result in higher
enhancement of compressive strength in the CN1-4 series-blended concrete. Also nano
ZnO2 recovers the nanoparticle-packing density of the blended cement, directing to a
reduced volume of larger pores in the cement paste.
The results show that the replacement of cement by nano ZnO2 in CNx-LW series
produces concrete with high strength with respect to CNx-W series.
Lime reacts with water and produces Ca(OH)2 which needs to form C-S-H gel
(Mostafa and Brown, 2005):
CaO + H 2 O = Ca(OH) 2 + Heat (1)

When nano ZnO2 react with Ca(OH)2 produced from saturated limewater, the content of
C-S-H gel is increased because of high free energy of nanoparticles which reduces
significantly when reacts by Ca(OH)2 (Nazari and Riahi, 2011).
The compressive strength of CN-W and CN-LW series should be compared from two
viewpoints. The first viewpoint is that the compressive strength of CN-W and CN-LW
series increases by partial replacement of cement with nano ZnO2 up to 4wt%. Once
more, this confirms the more C-S-H gel formation in the presence of saturated limewater
in which the quantity of nano ZnO2 (pozzolan) present in the mixture sample is close to
the amount required to combine with the liberated lime during the process of hydration
thus leading to lesser silica leaching out with respect to the specimens cured in water.
Second viewpoint is that the difference between compressive strengths of the CN-W and
CN-LW series after 28 days of curing is relatively high while this difference in
compressive strength after 90 days of curing is not high. This may be due to formation of
crystalline Ca(OH)2 in CN-LW series after 28 days causes reduction in compressive
strength. In other words, curing of the nano ZnO2 blended concrete in saturated limewater
after 28 days is completely suitable to achieve high strength especially with high weight
percent of nanopowders (Nazari and Riahi, 2011).
The results of saturated water absorption at different ages of moist curing are shown
in Table 4.
 Effect of nano ZnO2 and lime water curing on strength and water 363

Table 4 Percentage of water absorption for different mixtures (wt%)

Sample ID 7 days 28 days 90 days

CN0-W 5 4.2 3.5
CN1-W 4.6 4.1 3.4
CN2-W 4.1 3.5 2.9
CN3-W 3.4 2.8 2.4
CN4-W 2.9 2.5 2.2
CN0-LW 4.8 4.3 3.4
CN1-LW 4.6 3.8 3.1
CN2-LW 3.8 3.3 2.7
CN3-LW 3.1 2.7 2.3
CN4-LW 3.0 2.6 2.2

As it can be seen, the percentage of water absorption of concrete samples immersed

in water and saturated limewater decreases with the increase in the age of moist
curing from 7 to 90 days for all series during the hardening process of the concrete.
In the other words, C-S-H gel formation in the presence of nanoparticles especially for
the specimens cured at saturated limewater are high enough to reduce the water
absorption of the blended concrete. This reduction is more for CN-LW series as a
result of more C-S-H gel formation. However, this difference is not too high because of
this fact that the water permeability is significantly related to the content of pores in the
concrete which is equal for two CN-W and CN-LW series at a certain nanoparticle
content.
It was observed that the reduction of water absorption was found at the seven days of
curing higher for CN1-4 series compared to CN0 series. The decrease in water absorption
which is related to the increase in the amount of nano ZnO2 can be resulted from the
reduced amount of pores. These results were achieved because of fewer hydration
products when the pozzolanic reaction is small at the early ages for CN0 series reverse of
the CN1-4 series. On the other hand, the percentage of water absorption related to the
porosity of the hardened concrete which is engaged by water in saturated state (AI-Khalaf
and Yousift, 1984) was more in series CN0 compared to CN1-4 series at the early ages.
Nevertheless by increasing the age of curing to 90 days, the percentage of water
absorption values decreases significantly with the increase in nanoparticles content up to
4wt%. Therefore, it can be suggested that with prolonged curing, increasing the ages and
percentages of nano ZnO2 in both series can lead to reduction in permeable voids. This is
due to the pozzolanic action of nano ZnO2 and filler effect provided by both series of
nano ZnO2. Another finding is that the interfacial transition zone in concrete was
improved due to pozzolanic reaction as well as filler effect of the nano ZnO2, being also
confirmed by the reported results of Bui et al (2005).
364 F. Vazinram et al.

4 Conclusions

The results show that the nano ZnO2 blended concrete had higher compressive strength
compared to that of the concrete without nano ZnO2. It is found that the cement could be
advantageously replaced with nano ZnO2 up to 4 wt% when the specimens cured in water
and saturated limewater. Longer period of curing enhanced the strength and water
resistance of concrete specimens and higher improvement was achieved by curing in
saturated lime water. This could was explained by C-S-H gel formation in the presence of
nanoparticles especially for the specimens cured at saturated limewater being high
enough to reduce the water absorption of the blended concrete.

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