State-Of-The-Art Report On Use of Nano-Materials in Concrete

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State-of-the-art report on use of nano-materials in concrete

Article  in  International Journal of Pavement Engineering · November 2013


DOI: 10.1080/10298436.2014.893327

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State-of-the-art report on use of nano-materials in


concrete
a b b b
Md. Safiuddin , Marcelo Gonzalez , Jingwen Cao & Susan L. Tighe
a
School of Architectural Studies and Angelo Del Zotto School of Construction Management,
George Brown College, 160 Kendal Avenue, Toronto, Ontario, Canada M5T 2T9
b
Centre for Pavement and Transportation Technology (CPATT), Department of Civil and
Environmental Engineering, University of Waterloo, 200 University Avenue West, Waterloo,
Ontario, Canada N2L 3G1
Published online: 14 Mar 2014.

To cite this article: Md. Safiuddin, Marcelo Gonzalez, Jingwen Cao & Susan L. Tighe (2014): State-of-the-art report on use of
nano-materials in concrete, International Journal of Pavement Engineering, DOI: 10.1080/10298436.2014.893327

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International Journal of Pavement Engineering, 2014
http://dx.doi.org/10.1080/10298436.2014.893327

State-of-the-art report on use of nano-materials in concrete


Md. Safiuddina*, Marcelo Gonzalezb, Jingwen Caob and Susan L. Tigheb
a
School of Architectural Studies and Angelo Del Zotto School of Construction Management, George Brown College, 160 Kendal Avenue,
Toronto, Ontario, Canada M5T 2T9; bCentre for Pavement and Transportation Technology (CPATT), Department of Civil and
Environmental Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, Canada N2L 3G1
(Received 8 November 2013; accepted 7 December 2013)

Nanotechnology application to concrete presents an innovative approach to improve concrete properties based on the ability
to manipulate the cementitious material at an atomic scale. This paper presents a review of the nano-materials that have been
used in concrete. The literature survey revealed that four nano-materials are most often used to modify concrete properties;
these include nano-silica (nano-SiO2), nano-titanium dioxide (nano-TiO2), carbon nano-tubes (CNTs) and carbon nano-
fibres (CNFs). All of these four nano-materials have shown improvement in many concrete properties. Both nano-TiO2 and
nano-SiO2 reduce bleeding and segregation, and improve mechanical and transport properties. CNFs and CNTs tend to
adversely affect the fresh properties due to agglomerations, which are overcome when a surfactant or ultrasonic mixer is
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used. However, both CNFs and CNTs significantly improve the mechanical properties of concrete. This paper also discusses
how concrete durability is improved when nano-materials are added to concrete. In addition, this paper identifies several
research needs based on the gaps in the current state of knowledge on using nano-materials in concrete.
Keywords: concrete properties; durability; nanotechnology; nano-materials; nano-concrete

1. Introduction the particle size to nano-scale associated with high surface


According to the Cement Association of Canada (CAC), area can produce a significant impact on material
2.7 billion tons of cement was manufactured in the world properties.
to produce 9 billion cubic meters of concrete during In recent years, more interest is growing on the use of
2007 (CAC 2013). Concrete is the most widely used nano-materials in concrete. The literature survey reveals
material in the world due to its versatility, durability and that most of the studies conducted to date have focused on
sustainability. With the correct design and construction the use of nano-silica (nano-SiO2) (Shih et al. 2006,
process, users can obtain a service life of concrete over Quercia and Brouwers 2010, Said et al. 2012), nano-
50 years. titanium dioxide (nano-TiO2) (Diamanti et al. 2008, Chen
Regarding the constituent materials of concrete, the et al. 2012, Jalal et al. 2012), carbon nano-tubes (CNTs)
Strategic Development Council from the USA states that (Li et al. 2007a, 2007b, Mudimela et al. 2009) and carbon
there exists a variety of research needs to improve ‘energy nano-fibres (CNFs) (Toutanji et al. 1994, Mudimela et al.
efficiency, productivity, and the performance of concrete 2009) in concrete. In comparison, limited research
and concrete products’ (Strategic Development Council has been carried out to investigate the prospect of using
2002). These research needs may be categorised in three nano-iron (nano-Fe2O3), nano-alumina (nano-Al2O3),
groups: new materials, measurement and prediction, and nano-zirconium dioxide (nano-ZrO2), nano-lotus leaf,
reuse and recycling. Nano-materials can be considered in nano-slag, nano-fly ash, nano-cellulose and nano-clays.
the group of new materials. This paper presents an extensive review on the use of
The applicability of nanotechnology in a variety of nano-materials in concrete. The key aspects of nano-
fields is receiving additional attention (Gopalakrishnan concrete, the use of different nano-materials, and the
et al. 2011). Nanotechnology involves manipulating effects of the major nano-materials on the properties and
matter and materials at scales below 100 nm. It is a durability of concrete are discussed in this paper.
revolutionary tool that allows us to take advantage of the
radically different material properties that appear on the
nano-scale (WIN 2012). Nano-scale is the boundary 2. Nano-materials and nano-concrete
between atoms and molecules. The fundamental behavior The application of nanotechnology in concrete is still in its
and associated properties of materials are dictated at the infancy, but it has been recognised that nano-particles can
atomic scale (Ashby et al. 2009). Therefore, a reduction in be used to produce nano-concrete with enhanced concrete

*Corresponding author. Email: safiq@yahoo.com


q 2014 Taylor & Francis
2 Md. Safiuddin et al.
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Figure 1. Specific surface area of different constituent materials used in conventional concrete, high-strength/high-performance
concrete and nano-concrete. Source: Adapted from Ashby et al. (2009).

performance (Ashby et al. 2009). According to research in crystalline or amorphous structure (Bensted and Barnes
recent years, nano-concrete is defined as a concrete made by 2002). It is well known that C–S–H gel controls the
Portland cement and cementitious particles with sizes strength and durability of concrete (Skinner et al. 2010). At
smaller than 500 nm (Balaguru and Chong 2008, Sanchez this time, no consensus exists regarding the atomic structure
and Sobolev 2010). The important reasons to apply of C–S–H and how C–S–H is able to develop strength.
nanotechnology on concrete are to control material behavior, Tylor (1997) described a model to characterise the atomic
achieve superior mechanical and durability performance, and structure of C–S–H based on X-ray diffraction and
to provide novel properties in concrete such as low electrical scanning electron microscope (SEM) testing. The research
resistivity, self-sensing capability, self-cleaning and self- reported that C–S–H has an amorphous composition and
healing abilities, high ductility and self-control of cracks its nano-structure coincides with the 1.4 nm tobermorite
(Sanchez and Sobolev 2010). Because of the high surface layer structure. Moreover, according to Skinner et al.
area to volume ratio, nano-particles can act as nuclei for (2010), C–S–H can be characterised by a nanocrystalline
cement phases, providing excellent chemical reactivity to structure, represented closely by 1.1 nm tobermorite.
promote cement hydration. Figure 1 shows the range of Nanotechnology allows us to improve the under-
specific surface area for different materials used in concrete. standing of the C–S–H atomic structure. According to
This figure also provides the definition of nano-concrete Skinner et al. (2010), this new knowledge permits scientists
(nano-engineered concrete) (Ashby et al. 2009). to manipulate the C –S–H structure and therefore design
Concrete undergoes different phases during hydration concrete with enhanced properties. Based on nanotechnol-
where nano-materials can play a significant role. The ogy, Selvam et al. (2009) explained that electrostatic forces
different hydration characteristics of concrete are presented and bond forces in the silicate chains are mainly responsible
in Table 1. Calcium silicate hydrate (C–S–H) is the main for strength development in the C–S–H atomic structure.
product from the hydration process and presents a poorly Therefore, nanotechnology can play a significant role in

Table 1. Hydration characteristics of Portland cement concrete (w/c ¼ 0.5).

Approximate
Physical/chemical component volume (%) Comments
C– S– H 50 Includes gel pores; poorly crystalline/amorphous
structure
Calcium hydroxide (CH) 12 Crystalline structure
Ettringite and monosulphate phases (AFm and AFt phases) 13 Crystalline structure
Unreacted cement particles 5 Based on the hydration process
Capillary pores 20 Dependant of w/c
Source: Adapted from Bensted and Barnes (2002).
International Journal of Pavement Engineering 3

explaining the mechanisms of cement hydration in in a wide range of applications such as paints, cosmetics
concrete. Furthermore, nanotechnology may contribute to and drugs because of its low toxicity, semi-conductivity,
sustainable development. It has been reported that the high chemical stability, availability and low industrial
manufacturing of 1 ton of Portland cement produces about cost (Hamdy and Ion 2011). TiO2 can also be supplied as
1.0–0.8 ton of CO2 that causes adverse effect on the nano-TiO2, which is most widely used as a photo-catalyst
environment (Skinner et al. 2010). Enhancement of due to its extraordinary photo-catalytic activity (Chen et al.
concrete properties and durability would compensate this 2012). It has also been used in concrete (Diamanti et al.
adverse effect and thus the use of nano-concrete could be a 2008, Chen et al. 2012, Jalal et al. 2012).
strong motivation towards environmental sustainability.

3. Different types of nano-materials for concrete


The literature survey revealed that mostly four nano- 3.3 Carbon nano-tubes
materials, namely nano-SiO2, nano-TiO2, CNTs and CNTs were discovered in Japan by Sumio Ijima during
CNFs, have been used in concrete. transmission electron microscopy observation in 1991
(Ashby et al. 2009). The discovery was accidental while an
electrical discharge occurred between two carbon electro-
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3.1 Nano-silica des. CNTs can be defined as cylindrical molecules with a


Nano-SiO2 is a widely used nanomaterial in concrete. The nano diameter (1 nm to a few nanometers) and a length
main chemical component of nano-SiO2 is silicon dioxide lower than few micrometers. CNTs are made of carbon
(SiO2); it can be present in crystalline and amorphous atoms interconnected together by carbonZcarbon (CZC)
forms. The amorphous nano-SiO2 is most commonly used bonds (Rashid 2012). Based on the manufacturing
in nano-concrete (Quercia et al. 2012). Nano-SiO2 presents conditions, CNTs can be generated as single-walled,
sphere morphology and its particles size is variable. double-walled or multi-walled. The hexagonal structure of
According to Quercia and Brouwers (2010), the particle size the carbon lattice in the CNTs provides a very strong
varied in the range of 5–658 nm in six different nano-SiO2 structure. The morphology of single-walled CNT
products. Nano-SiO2 is available in powder and slurry forms. (SWCNT) and multi-walled CNT (MWCNT) is presented
The slurry form is attractive in order to avoid health problems in Figure 3. MWCNTs are less expensive and more readily
associated with ingesting the powder. Figure 2 presents an available than SWCNTs (NRCC 2013).
SEM image of a commercially available nano-SiO2, where CNTs exhibit several key engineering properties
the sphere morphology is very clear. including very high Young’s modulus of 1000 GPa,
high tensile strength of 30 GPa, superior current density
of 109 A/cm2 and high thermal conductivity of 6000 W/mK
3.2 Nano-titanium dioxide (Ashby et al. 2009). CNTs possess better material
Titanium dioxide (TiO2) is the naturally occurring oxide of properties than CNFs and according to the National
titanium. In nature, it is present in the following minerals: Research Council of Canada (NRCC), they are ideal
rutile, anatase and brookite. TiO2 has historically been used reinforcing materials for concrete (NRCC 2013).

Figure 2. Transmission electron micrographs of nano-SiO2.


4 Md. Safiuddin et al.

4. Effects of nano-materials on different


properties of concrete
Based on the literature review, nano-materials influence
both the fresh and hardened properties of concrete. The
effect of nano-materials on the fresh properties, cement
hydration, microstructure, pore-structure, mechanical
properties, transport properties and durability of concrete
has been summarised in the following sub-sections.

4.1 Effects on fresh concrete properties


Figure 3. Single-walled and multi-walled CNTs. Source: The fresh properties of concrete are affected by the particle
Adapted from Rashid (2012).
size distribution of constituent materials. Therefore, nano-
materials are expected to influence the fresh concrete
properties due to their extremely small particle sizes. The
3.4 Carbon nano-fibres research findings of Quercia and Brouwers (2010) and
CNFs play a very significant role in cement concrete Gonzalez et al. (2013) showed that nano-SiO2 significantly
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because of its extraordinary and useful properties, such as reduces the workability of concrete for given water content
exceptional tensile strength, high stiffness, low density, due to high specific surface area. A similar effect was also
good chemical stability, and high electrical and thermal observed in the case of nano-TiO2 (Chen et al. 2012).
conductivity (Zhang et al. 2007, Mudimela et al. 2009). This suggests that the water demand is strongly related
CNFs have cylindrical nanostructures with diameters less with the specific surface area of nano-materials. Quercia
than 100 nm. Also, Tyson et al. (2011) reported that CNFs and Brouwers (2010) stated that a higher amount of water
possess a Young’s modulus of 400 GPa and a tensile is needed for a constant workability when the surface area
strength of 7 GPa. According to Gay and Sanchez (2010), of nano-SiO2 is increased. Therefore, high-range water
CNFs have a lower production cost than CNTs and reducing admixture or superplasticiser is required to
therefore their use in concrete could be cost-effective. maintain the target workability of concrete (Gonzalez
The improvement in the engineering properties of nano- et al. 2013) when the water content is kept unchanged, as
concrete cannot be guaranteed based only on the excellent obvious from Figure 5. The air-void stability of concrete is
material properties of CNFs and CNTs. This is because the also affected in the presence of nano-SiO2. Hence, a higher
properties of these nano-materials are influenced by two dosage of air-entraining admixture is needed for a given air
other important factors; firstly, the nano-filaments must be content of concrete (Gonzalez et al. 2013), as can be seen
dispersed in the paste matrix and secondly, the bond from Figure 5. It should also be mentioned that the demand
strength between the matrix and surface of CNFs or CNTs for both high-range water reducing admixture and air-
must be achieved. The proper dispersion of CNFs (Figure 4) entraining admixture increased linearly with the higher
can be achieved in nano-concrete or nano-composite by percentage of nano-SiO2 in concrete. This is evident from
engineering the mixing process. Figure 5. Moreover, because nano-SiO2 produces higher

7000
AEA
6000 HRWRA

5000
Dosage (ml/m3)

CNF 4000

3000

2000

1000

0
CC (0.0%Nanosilica) NSC 1 (0.5% NSC 2 (1.0% NSC 3 (1.5%
Nanosilica) Nanosilica) Nanosilica)
Type of concrete

CNFs in cement paste matrix


Figure 5. Air-entraining admixture (AEA) and high-range water
reducing admixture (HRWRA) demands for nano-concrete with
Figure 4. Scanning electron micrograph of CNF-composite. different nano-SiO2 contents. CC: conventional concrete; NSC:
Source: Adapted from Gay and Sanchez (2010). nano-silica concrete. Source: Adapted from Gonzalez et al. (2013).
International Journal of Pavement Engineering 5

plasticity than traditional cementitious materials, it can materials has been shown in Figure 1. Because of low
improve the cohesiveness of the concrete and thus reduce particle size and high surface fineness, nano-SiO2
the bleeding and segregation (Quercia and Brouwers 2010). contributes to the creation of small-size crystal and
Nano-materials can significantly influence the rheology clusters of C – S –H during pozzolanic reaction.
and stability of concrete. According to Jalal et al. (2012), Like nano-SiO2, adequately dispersed SWCNT can
nano-TiO2 is able to modify the rheological properties of also accelerate the hydration process in cement paste
self-compacting concrete. The rheological properties were (NRCC 2013). This is possibly due to SWCNTs appearing
studied through slump flow, V-funnel flow and L-box tests. to act as nuclei for C3S (tricalcium silicate) hydration
Nano-TiO2 powder improved the consistency and homogen- reaction, with the C – S – H forming directly on the
eity of the fresh concrete mixture, with less bleeding and SWCNT. Moreover, SWCNTs produce an increase in
segregation. This can be explained by the fact that nano-TiO2 the maximum heat flow. This may also enhance the
acts as a filler in the mixture and improves the resistance to hydration of cement in concrete. Furthermore, the
water movement in fresh concrete. incorporation of nano-TiO2 in powder form can signifi-
Certain nano-materials might influence the setting of cantly accelerate the rate and degree of hydration at early
concrete. For example, the higher nano-TiO2 content and stages; it can promote the formation and precipitation of
fineness decrease the setting time of concrete. This is hydration products (Chen et al. 2012).
related to acceleration of the hydration process and
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associated heat release. Hydration heat peak increases


when the nano-TiO2 is added into the cement. The particle 4.3 Effects on microstructure and pore-structure of
fineness and specific surface area play a dominant role in concrete
enhancing the dissolution rate of cement compounds at the Nanoparticles can potentially allow better void filling and
early stage of cement hydration, thus increasing heat other positive filler effects due to the extremely low
release (Chen et al. 2012). particle size in comparison with conventional cementing
Nano-materials may cause adverse effects on the fresh materials of concrete (Ashby et al. 2009); the filler effects
properties of concrete if they are not dispersed properly. produce a concrete microstructure with improved density
More specifically, dispersion issues with CNFs and CNTs and reduced porosity (Sanchez and Sobolev 2010).
were reported by several authors (Gay and Sanchez 2010, According to Ashby et al. (2009), nanoparticles organised
NRCC 2013, Rashid 2012). Overall, it is difficult to themselves in an efficient close-packed configuration. In
achieve homogeneous dispersion of CNTs and CNFs in geometry, close-packing of similar spheres is a dense
concrete mixture (Nasibulina et al. 2010). These nano- arrangement of congruent spheres in an infinite and regular
materials are prone to affect the fresh concrete properties arrangement. He and Shi (2008) explained that nanoma-
due to agglomerations. The attraction between particles of terials can act as fillers creating a dense and less permeable
CNFs/CNTs due to Van der Waals forces might be mortar microstructure; also they may act as nuclei to
responsible for agglomerations. However, the use of a facilitate the creation of hydration products and thus may
surfactant or ultrasonic mixer allows for adequate promote the formation of high-density C –S – H structures.
dispersion. Also, the use of high-range water reducing Hosseini et al. (2011), Said et al. (2012) and Ji (2005)
admixture was successful in disaggregating the CNFs, thus observed such effects in the case of nano-SiO2. Ji (2005)
improving the dispersion of nano-fibres in the cement showed the improvement of microstructure of concrete
matrix (Gay and Sanchez 2010). including nano-SiO2 based on the field emission scanning
electron microscope (FESEM) test. It was concluded that
the addition of nano-SiO2 can make the microstructure of
4.2 Effects on cement hydration concrete more uniform and compact than normal cement.
The incorporation of nano-materials such as nano-SiO2, In 2010, Hosseini et al. (2010) carried out an experimental
CNTs and nano-TiO2 can positively influence the study to explain the modification of concrete microstruc-
hydration reactions and the physical structure of C –S – H ture in the presence of nano-SiO2. They summarised that
in cement (He and Shi 2008, NRCC 2013, Chen et al. nano-SiO2 contributes to improve concrete microstructure
2012). Using a field emission scanning electron micro- in four ways: (a) acting as a nucleus, (b) generating better
scope (FESEM), He and Shi (2008) explained that nano- C –S – H, (c) controlled crystallisation and (d) filling of
SiO2 not only makes a dense material but also can change micro-voids.
the morphology of hydrated cement by producing more The replacement of a certain amount of cement with
C – S– H gel and less ettringite crystals. According to nano-SiO2 decreases the porosity of concrete (Mondal
Ashby et al. (2009), the drastic increase in surface area of et al. 2010, Shirgir et al. 2011, Said et al. 2012). The
nano-SiO2 can affect the surface energy, morphology and concrete mixtures with nano-SiO2 have less threshold pore
the chemical reactions in concrete. The high specific diameter than the control mixtures without nano-SiO2 (Lin
surface area of nano-SiO2 compared with other concrete et al. 2008a, 2008b, Said et al. 2012). Also, nano-SiO2
6 Md. Safiuddin et al.

results in a better pore structure refinement in concrete higher strength in concrete (Mondal et al. 2010). Due to
(Said et al. 2012). more particle and surface fineness, nano-SiO2 is more
The porosity of concrete is also decreased when nano- effective than microsilica to increase the compressive
TiO2 is used with cement. Nano-TiO2 can modify the pore strength. Furthermore, the addition of nano-TiO2 up to
size distribution and decrease the total pore volume by 3 wt% can significantly increase the compressive strength
filling up the pore space around them gradually as of concrete by forming a larger amount of hydration
hydration continues (Chen et al. 2012). Zhang and Li products (Ali and Shadi 2011, Chen et al. 2012).
(2011) and Ali and Shadi (2011) found that the pore Not only compressive strength, nano-materials can
structure of concrete containing nano-TiO2 is finer than also improve the flexural strength of concrete. Gopalak-
that containing nano-SiO2. Therefore, the concrete rishnan et al. (2011) reported that nano-SiO2 increases
containing nano-TiO2 can exhibit a higher resistance to both the compressive and flexural strengths of concrete.
the penetration of deleterious agents than the concrete Similar results were also observed by Hosseini et al.
containing nano-SiO2. (2010) as shown in Figure 7. The other nano-materials
such as nano-TiO2 and CNFs also significantly improve
the compressive and flexural strengths of concrete (Li et al.
4.4 Effects on mechanical properties of concrete 2004, 2006, Metaxa et al. 2010).
Nano-materials improve the mechanical properties of Metaxa et al. (2010) tested the flexural strength of the
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concrete due to improved particle packing and better concrete samples reinforced with 0.025%, 0.048%, 0.08%
bonding. According to Quercia and Brouwers (2010), the and 1% CNFs by weight of cement. They concluded that
properties of hardened concrete are governed by the the optimal content of CNFs is 0.048 wt%, which provides
overall grading of the solid materials. The increase in the the strength increase up to 45%. Also, they mentioned that
particle size range including very small solid particles with CNFs ensure the full capacity of the fibres to transfer the
dimensions below 300 nm improves particle packing. load due to excellent bonding between the nano-fibres and
Based on the analysis of six commercial nano-SiO2 the cement hydration products. Furthermore, the test
products, Quercia and Brouwers (2010) reported that results from Zhou et al. (2009) showed that the Young’s
nano-SiO2 is a suitable alternative to improve grading modulus of CNFs and the tensile strength can reach up to
since its particle size ranges from 5 to 658 nm. In addition, 600 MPa and 60 GPa, respectively. According to the report
nano-materials result in an improvement in aggregate/ of Li et al. (2005), the addition of CNTs can also increase
paste contact zone, thus producing a better interfacial bond the flexural and compressive strengths of concrete. This
between aggregate and cement paste (Gopalakrishnan improvement is related to the modification of the concrete
et al. 2011). microstructure from three aspects: (a) CNTs interact with
Several studies indicated that the addition of nano- hydrates to produce a high bonding strength and increase
SiO2 in cement paste can improve the compressive the load transfer capacity, (b) CNTs reduce the total pore
strength of concrete due to its high surface area and volume in bulk cement paste, thus increasing the strength
pozzolanic effect (Ji 2005, Shih et al. 2006, Flores et al. of concrete and (c) CNTs treated with H2SO4 and HNO3
2010, Said et al. 2012, Gonzalez et al. 2013), as evident mixture solution act as the bridge connection between
from Figure 6. It is already recognised from the past cracks and voids (Figure 8) to enhance the tension load
research that silica fume (micro-silica) can result in a

100 8

90 7 Days 7
Compressive strength (MPa)

Flexural strength (MPa)

80 28 Days
6
70
5
60
50 4
40 3
30
2
20
10 1

0 0
CC(0.0% NSC1(0.5% NSC2(1.0% NSC3(1.5% CC (0%Nanosilica) NSC 1 (1% NSC 2 (2% NSC 3 (3%
Nanosilica) Nanosilica) Nanosilica) Nanosilica) Nanosilica) Nanosilica) Nanosilica)
Type of concrete Type of concrete

Figure 6. Compressive strength for different concretes Figure 7. Flexural strength of nano-SiO2 concrete. CC:
including nano-SiO2. CC: conventional concrete; NSC: nano- conventional concrete; NSC: nano-silica concrete. Source:
silica concrete. Source: Adapted from Gonzalez et al. (2013). Adapted from Hosseini et al. (2010).
International Journal of Pavement Engineering 7

which means that the incorporation of nano-SiO2 can


effectively decrease the degradation rate to improve
concrete durability (Gaitero et al. 2008).
The incorporation of nano-materials such as nano-
Fe2O3, nano-Al2O3, nano-TiO2, nano-SiO2 and nano-clays
(montmorilonite) improves the chloride penetration
resistance of the mortar phase of concrete (He and Shi
2008). Particularly, a small amount of nano-SiO2 and
nano-clays significantly enhanced the chloride penetration
resistance. A similar finding was obtained from other
research: according to Shekari and Razzaghi (2011), a
Figure 8. Scanning electron micrograph of cracked CNT- constant amount (1.5 wt% of cement) of nano-ZrO2, nano-
composite. Source: Adapted from Sanchez and Sobolev (2010). Fe2O4, nano-TiO2 and nano-Al2O3 showed a reduction of
chloride penetration in the range of 20 –80%. Moreover,
Said et al. (2012) reported that the rapid chloride
transfer, thereby improving the flexural strength of permeability significantly decreased when nano-SiO2
concrete. was added into the concrete mixtures. They concluded
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Some nano-materials can significantly improve the that a small amount of nano-SiO2 can provide a significant
toughness of concrete along with other properties. Rashid effect on reducing the penetration of chloride ions into
(2012) state that the ultimate strain capacity increases by concrete.
142%, the flexural strength increases by 79% and the Nano-materials can substantially decrease the water
fracture toughness increases by 242% when a small permeability of concrete. It has been reported that nano-
amount of CNT (0.1%) is incorporated into concrete. SiO2 reduces the water permeability because it improves
These results show that CNTs produce significant the microstructure of concrete with compact pore-structure
enhancement in the mechanical properties of concrete. (Ji 2005, Shirgir et al. 2011, Said et al. 2012). The water
Nano-materials can also improve some of the other permeability of matured concrete is also reduced due to the
properties of concrete. Li et al. (2006) reported that nano- excellent packing condition of nano-TiO2, which can
TiO2 significantly enhances the flexural fatigue perform- provide a better compacted and refined pore structure
ance of concrete. In their study, the concrete with 1% nano- (Jalal 2012).
TiO2 by weight of binder exhibited the best flexural fatigue A recent study has also shown that the water
performance. In this case, the fatigue life was increased by absorption decreases when nano-materials such as nano-
475.38% and 267.22% at the stress levels of 0.85 and 0.70, SiO2 are used in concrete (Jalal and Noorzad 2012). The
respectively (the stress level was defined by the quotient authors reported that an addition of 2% nano-SiO2
between flexural fatigue strength and flexural strength). results in a reduction of 58% and 54% capillary water
absorption at the age of 3 days for the binder content of
400 and 500 kg/m3, respectively. It has been summarised
4.5 Effects on transport properties and durability of that the concrete containing nano-SiO2 possesses a more
concrete packed microstructure, and thus exhibits less capillary
Durability is the goal of any agency to ensure a sustainable absorption (Jalal and Noorzad 2012). Nano-TiO2 also
development of concrete infrastructure. Mondal et al. greatly decreases the water absorption of concrete
(2010) found that the addition of certain nano-materials (Jalal 2012).
such as nano-SiO2 can significantly improve the durability Nano-materials improve the abrasion resistance of
of concrete. Calcium hydroxide crystals remain in the concrete. Abrasion is a definite distress on concrete surface
pores of concrete when pH . 12.5 (Mondal et al. 2010). If that may affect floors, pavements and hydraulic structures
the environmental condition lowers the pH, the equili- (CAC 2012). Therefore a concrete with high abrasion
brium will be disturbed, and it will cause leaching of Ca resistance is desirable. According to Gopalakrishnan et al.
(OH)2 from the concrete. The leaching of Ca(OH)2 makes (2011), nano-materials can enhance the abrasion resistance
concrete microstructure porous and thus affects its of concrete. Abrasion resistance is substantially improved
durability. The concrete durability is improved with the when nano-materials are added to concrete, as obvious
reduction in calcium leaching. From the magic angle from Figure 9. This figure shows the abrasion resistance
spinning-nuclear magnetic resonance spectra of the index which is defined by the quotient between the square
cement pastes with nano-SiO2, it was observed that root of the head revolutions and the depth of abrasion
nano-SiO2 can increase the amount and strength of high- grooves. The abrasion resistance of concrete can be
stiffness C –S – H (Mondal et al. 2010). The high-stiffness increased by up to 157% when 1% nano-SiO2 by weight of
C – S– H provides a higher resistance to calcium leaching, cement is used in concrete mixture. The abrasion
8 Md. Safiuddin et al.

3.0 Nano-material is indeed a valuable technology that can


be very useful for many kinds of application. However,
2.5
there still exist several implications that must be
Index of abrasion resistance

2.0 considered to enhance the use of nano-materials. These


are related to the prospects of nano-materials and the risks
1.5
associated with their use in concrete (Ashby et al. 2009).
1.0 In concrete material applications, construction procedures
can adapt techniques to minimise or eliminate health risks
0.5
(Birgisson et al. 2010).
0.0
Conventional concrete Nano-silica concrete Nano-titanium concrete
Type of concrete
7. Research needs
Figure 9. Abrasion resistance for different nano-concretes.
Source: Adapted from Gopalakrishnan et al. (2011). Significant gaps in the current state of knowledge have
been found from the literature survey on the use of nano-
materials in concrete. The following research needs have
resistance of concrete can be increased by 180.7% when
been identified based on the present study:
1% nano-TiO2 by weight of cement is used.
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. Substantial research has been carried out using


nano-SiO2 in concrete. The researchers emphasised
5. Cost-effectiveness of nano-materials the effect of nano-SiO2 on a number of fresh
properties, hardened properties and durability of
The construction industry is sensitive to the direct cost of
concrete. However, limited studies examined the
construction. Currently, the use of nano-materials is cost-
effect of nano-SiO2 on the air content, shrinkage and
prohibitive because of the high initial cost. However, more
skid resistance of concrete. Also, it is still not clear
demand will reduce the cost of nano-materials (Ashby
whether pozzolanic effect or high specific area of
et al. 2009). In addition, the project cost must be evaluated
nano-SiO2 is the main reason for improvement of
based on the life-cycle assessment since nano-materials
compressive strength in nano-silica concrete. More
would increase the durability of concrete structures. This
studies are needed to answer this question.
means less maintenance cost and less materials usage
. Significant interest has grown on the potential use of
because of a reduction in the maintenance/rehabilitation
CNTs and CNFs because of their excellent
interventions. Hence, the use of nano-materials can be
engineering properties and self-healing effect on
cost-effective in the long run, despite the high initial cost.
nano-cracks in concrete. Most of the studies showed
that it can improve the strength and durability-
related (transport) properties of concrete. But fewer
6. Health risks of using nano-materials in concrete studies research their effects on fresh properties and
Nanotechnology has the potential for innovations in durability performance (freeze – thaw resistance,
construction industry. However, there are reasonable resistance to sulfate attack, resistance to alkali-
apprehensions that nano-materials could cause health aggregate reaction, etc.).
damages if not used cautiously (Ashby et al. 2009). Since . Some studies have already been done regarding the
nano-material consists of ultrafine particles with nano- effects of nano-TiO2 on the fresh properties,
scale dimensions (# 100 nm), there are health risks due to porosity, permeability, hydration, compressive
the possible inhalation of nano-particles. Napierska et al. strength and fatigue performance of concrete. Yet,
(2010) reported that ultrafine particles (, 0.1 mm) have more studies are required to investigate the effect of
been revealed to cause dangerous inflammatory reactions nano-TiO2 on the shrinkage, skid resistance and
and lung damages, even more than fine particles of less durability of concrete.
than 2.5 mm size. Due to very small particle size, nano- . There are some other nano-materials such as nano-
particles have the ability to increase the cell penetration, Fe2O3, nano-Al2O3, nano-ZrO2, nano-montmorillo-
thus they are more likely to promote biological effects. nite, nano-cellulose and nano-lotus leaf that can be
Several adverse health effects, such as lung cancer, used in concrete. However, only a few studies have
silicosis, chronic obstructive pulmonary disease are been carried out to utilise these nano-materials in
mainly related to crystalline silica (for example, quartz concrete. More research should be carried out to
and cristobalite). Amorphous silica such as diatomaceous examine the potential effects of these nano-materials.
earth is considered less detrimental to health (Napierska . In terms of concrete durability in cold regions, the
et al. 2010). Nano-SiO2 that has been used significantly in resistance to freezing and thawing must be evaluated
producing nano-concrete contains an amorphous structure. because there is limited information on the freeze –
International Journal of Pavement Engineering 9

thaw performance of nano-materials. In addition, the (NSERC) and the Cement Association of Canada (CAC),
effects of nano-materials on the resistance to alkali- particularly Rico Fung who is the Director of CAC’s Markets and
Technical Affairs in Ontario. The authors are also thankful to
aggregate reactions and sulfate attack have not been
Gloria Stephens, Physiotherapist from South Metropolitan Area
investigated. Public Health Care Service (Health Ministry of Chile) for her
. Most studies evaluated the performance of nano- advice about health risks of using nano-materials.
materials based on laboratory results. It is necessary
to verify the field performance in real projects in
order to obtain experience regarding the application References
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