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