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Chapter 29
Applications of Nanotechnology
in Cement and Concrete Science
Salim Barbhuiya
Curtin University of Technology, Australia

Muneeb Qureshi
Curtin University of Technology, Australia

ABSTRACT
The properties of concrete are strongly influenced by the properties of its components and hydrates at
the nanoscale. Therefore, application of nanotechnology in cement and concrete science will engender
new opportunities for improvement of strength and durability of concrete. The objective of this chapter
is to advance the science and engineering of nanotechnology in modifying and monitoring the behaviour
and performance of cement and concrete at the nanoscale. The chapter assists in the identification of
promising new research and innovations in concrete materials using nanotechnology that can result in
improved mechanical properties, volume change properties, durability, and sustainability. The chapter
also provides a unique base for scientists, engineers, and practitioners to help set the future direction
of the use of nanotechnology in cement and concrete science.

INTRODUCTION characterizing and checking components at the

Nanotechnology is an appearing field of research
associated to the understanding and command of
issue at the nano scale, i.e., at dimensions between
approximately 1 and 100 nm. At the nano scale,
unique phenomena endow novel submissions.
Nanotechnology encompasses nano scale science,
technology, and expertise that engage imaging,
measuring, modelling, and manipulating issue at
this extent scale. Nano scale particles are not new
in either environment or research. Latest develop-
ments in visualization and estimation systems for
nano scale have led to a blast in nanotechnology-
based components in areas such as polymers,
plastics, electronics, vehicle constructing and
surgery (Duncan, 2011). Issue can display unusual
physical, chemical, and biological properties at the
nano scale, differing in significant ways from the
properties of bulk components and single atoms or
substances. Some nanostructured components are
more powerful or have distinct magnetic properties
contrasted to other forms or sizes of the identical
material. Others are better at carrying out heat or
electricity (Ma et al., 2008). They may become

DOI: 10.4018/978-1-4666-6363-3.ch029

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Applications of Nanotechnology in Cement and Concrete Science

more chemically reactive or contemplate light nanotechnology or molecular constructing

better or change colour as their dimensions or
structure is changed (Baddeley et al., 2007).
Working at the nano scale endows scientists to
utilize the unique personal, chemical, mechanical,
and optical properties of components that routinely
occur at that scale. Specific relevance for solid is
the greatly advanced surface locality of particles
at the nano scale. As the surface area per mass
of a material rises, a greater amount of the mate-
rial can arrive to communicate with surrounding
materials, therefore affecting reactivity. Nanotech-
nology considers two major advances as shown
in Figure 1: the top down approach in which
bigger organisations are decreased in dimensions
to the nano scale while sustaining their original
properties without atomic-level control (e.g.,
miniaturization in the domain of electronics) or
deconstructed from bigger organisations into their
lesser composite components and the bottom-
up approach, furthermore called molecular
in which components are engineered from atoms
or molecular components through a method of
assembly or self-assembly.
The mechanical properties of cement and
concrete depend to a large extent on structural
elements and phenomena, which are effective
on a micro- and nanoscale (Shah et al., 2011).
Nanotechnology has the potential to engineer
concrete with superior properties through the
optimization of material behavior and performance
needed to significantly improve mechanical per-
formance, durability and sustainability. The use
of nanotechnology is likely to make various key
breakthroughs in cement and concrete technology.
Better understanding and precise engineering of
an extremely complex structure of cement-based
materials at the nano-level will result in a new
generation of concrete, stronger and more durable,
with desired stress-strain behavior and possibly
possessing the range of newly introduced smart

Figure 1. Top down and bottom up approaches in nanotechnology

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Applications of Nanotechnology in Cement and Concrete Science
properties. The advances in instrumentation and
computational science are enabling scientists and
engineers to obtain unprecedented information
about concrete, from the atomic through the con-
tinuum scale, and the role of nanoscale structures
on performance and durability. This information is
crucial for predicting the service life of concrete
and for providing new insights on how it can be
improved (Sanchez & Sobolev, 2010).
Better understanding and mimicking the pro-
cesses of bottom-up construction successfully
employed by nature is one of the most promising
directions in nanotechnology (Bhushan, 2004).
It was proved that the exceptional mechanical
performance of biomaterials, such as bones or
mollusk shells, is due to advanced nanostructure
and the reinforcing action of nanocrystals of
calcium compound. High tensile strength macro-
defect-free (MDF) cement is a polymer-cement
composite, which mimics the structure of the
abalone shells at the micrometer and nanometre
levels. Improved performance of MDF is attributed
to the grafting of polymer chains onto the surface
of cement grains.
NANO-MODIFICATION
OF CONCRETE
From nanotechnology point of view, hardened
cement itself is clearly a nanomaterial without
any modification. This is because it has a hier-
archical structure ranging from sub-millimetre
dimension down to nanometre scale. The general
view on length scale and surface areas related to
concrete making materials and additives is shown
in Figure 1. Moreover, it is also well established
that most of its material properties mainly depend
on the microstructural development below 100nm
(Taylor, 1997).
In the last decades there has been a continu-
ously increasing trend to modify and optimize
cementitious binders by means of nanotechnology
and nanoscale additives. Supramolecular additives
in cement and concrete are known and used since
626
the mid-1960s. They can act as high performance
dispersants, rheology modifier or anti shrinkage
agents. They control rheological properties of
the cement paste by electrostatic, hydrophobic or
steric interactions. The development of improved
supramolecular additives allowed incorporation
to a certain extent, nanoscale filler particles and
materials into cement paste and concrete mixes.
These fillers are mostly inert and they neither
interfere with the hydration process nor do they
change the hydration products. Their main task
is to optimize the grain size distribution leading
to a highly filled and compact cement matrix
with reduced pores and voids. The latest means
of nano-modification of cementitious systems
are functional nano additives, which influence
hydration and/or structure development. Known
systems comprise of nano-tubes or nano-rods
(Akkaya et al., 2003; Trettin & Kowald, 2005;
Shah et al., 2009), nanoscale C-S-H particles and
nanoscale gypsum particles. They act as internal
reinforcement as well as nucleation and crystal-
lization seeds.
SUPERHYDROPHOBIC CONCRETE
The leaves of the lotus plant (Nelumbo Nucifera)
naturally have superhydrophobic and self-cleaning
surfaces. This provides an excellent example of
how biomimetics can be used for an effective
engineering design (Bhushan, 2004). The superhy-
drophobicity of most plant surfaces is achieved by
hierarchical structures of convex or papilla epider-
mal cells with three-dimensional wax structures on
top. The hierarchical (double-structured) surface
is characteristic for the lotus leaf, which is built of
convex cells and has a much smaller superimposed
layer of hydrophobic, three-dimensional wax
tubules. Wetting of such surfaces is minimized,
because air is trapped in the cavities of the convex
cell and the hierarchical roughness enlarges the
water-air interface while reducing the solid-water
interface. Water on such a surface gains very little
energy through adsorption and forms a spherical

Applications of Nanotechnology in Cement and Concrete Science

droplet. Therefore, both the contact area and the
adhesion to the surface are dramatically reduced.
The superhydrophobic and self-cleaning surfaces
of a flowering plant of lotus (Nelumbo Nucifera)
is shown in Figure 3a; a lotus leaf contaminated
with clay is shown in Figure 3b; removal of the
adhering particles by water is shown in Fig 2c;
a spherical water droplet on a superhydrophobic
leaf is shown in Figure 3d; the SEM image of a
droplet (Figure 3e) illustrates the low wettability
of superhydrophobic microstructured surfaces;
the SEM images 3f, 3g and 3h show the Lotus
leaf surface in different magnifications (Koch et
al., 2008).
In concrete, superhydrophobicity can substan-
tially improve the performance of conventional
hydrophobic materials (e.g., siloxane-based, such
as polyethyl-/polymethyl- hydrosiloxane, PEHSO/
PMHS) and control the wettability of solid
materials (Sobolev & Batrakov, 2007). Super-
hydrophobic surfaces with a water contact angle
() larger than 150 (Figure 4) have generated
much interest due to their potential in industrial
applications (mainly for self-cleaning), and this
nature-inspired concept was recently realized for
enhancing concrete durability. To manufacture su-
perhydrophobic admixture the hydrogen contain-
ing siloxane (e.g., PEHSO/PMHS) is combined
with small quantities of super-fine, submicro- or

Figure 2. Particle size and specific surface area related to concrete making materials (Sobolev &
Ferrada-Gutirrez, 2005)

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Applications of Nanotechnology in Cement and Concrete Science

Figure 3. Superhydrophobic and self-cleaning surfaces of a flowering plant of lotus (Nelumbo Nucifera)

nano-sized particles such as nano-silica, nano-clay USE OF NANO PARTICLES

additives or SiO2-rich reactive powders (Sobolev
et al., 2011). The volume, size and distribution
of the air voids within the hardened cement
phase can be precisely tailored by preparing the
water-based PEHSO emulsion with a certain
droplet size. Submicro- or nano-sized particles
provide the micro-roughness within the pore
space, which plays an important role in forming
superhydrophobic surfaces within the hardened
cement and improves the self-healing potential of
concrete. The surfaces of the voids are covered by
the hydrophobic particles, providing the effect of
superhydrophobic hybridization.
AND NANO REINFORCEMENT
IN CONCRETE
Nanoparticles are gaining widespread attention
to be used in construction sector so as to exhibit
enhanced performance of materials in terms of
smart functions and sustainable features. Incor-
poration of various nanoparticles into the cement
matrix to improve various properties of concrete
emerged as a promising research filed of nano-
composites. In cement matrix, most of the research
to date was conducted on nano-silica (nano-SiO2)
(Bjornstrom et al. 2004; Li et al., 2004; Li et al.,

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Applications of Nanotechnology in Cement and Concrete Science

2006; Sobolev et al., 2009; Qing et al., 2008) and
nano-titanium oxide (nano-TiO2) (Li et al., 2006;
Li et al., 2007). A few studies on the incorpora-
tion of nano-iron (nano-Fe2O3) (Li et al., 2004),
nano-alumina (nano-Al2O3) (Li et al., 2006) and
nano-clay particles (Chang et al., 2007) in cement
matrix are also reported. Research (Sobolev &
Ferrada-Gutirrez, 2005) showed that nano-SiO2
(Figure 5) improves the workability and strength
of concrete.
The incorporation of nano-SiO2 in concrete
was also found to increase the water penetration
resistance of concrete (Ji, 2005). Gaitero et al.,
(2008) have demonstrated that use of nano-SiO2
can help to control the calcium leaching in con-
crete. It is also reported that nano-SiO2 is more
effective than microsilica in enhancing the strength
properties of concrete (Jo et al., 2007; Qing et
al., 2007). Particles of nano-SiO2 not only act as
a filler material, but also they act as an activator
to promote the pozzolanic reaction. Li (2004)
reported that significant increase in compressive
strength at early age could be obtained using
nano-SiO2 in high volume fly ash concrete, which
is one of the drawbacks of this type of concrete.
However, in order to achieve good performance
and to use nano-SiO2 in economical way, it is
better to use nano- SiO2 in a combination of fly

Figure 4. Concept of super-hydrophobic hybridization of concrete pore surface (Sobolev & Sanchez, 2012)

Figure 5. Spherical nano-SiO2 particles of uniform distribution observed using TEM (Sobolev & Ferrada-
Gutirrez, 2005)

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Applications of Nanotechnology in Cement and Concrete Science
ash and microsilica. According to Hosseini et al.,
(2010), nano-SiO2 improves the properties of the
cement matrix by (i) providing a nucleation site,
(ii) producing added amount of C-S-H gel through
pozzolanic reaction, (iii) controlling crystalliza-
tion and (iv) modifying the microfilling effect.
Nano-Al2O3 is very useful to modify the modu-
lus of elasticity of cement mix. The addition of
nano-Al2O3 was also found to be very effective to
increase the elastic modulus of mortar. With the
addition of 5% nano-Al2O3, Li et al., (2006) found
that there was an increase of 143% in the elastic
modulus. However, the authors reported that they
had a limited effect on the compressive strength.
Recent research by Barbhuiya et al., (2014) has
shown that proper dispersion is one of the major
problems in using nano-Al2O3. The SEM image
(Figure 6) of hydrated cement paste containing
2% nano-Al2O3 clearly shows the agglomeration
of nano-Al2O3. Nano-Fe2O3 is reported to provide
Figure 6. SEM image of cement paste of containing 2% nano-Al2O3 hydrated for 7 days (Barbhuiya et
al., 2014)
630
concrete the self-sensing capacity (Li et al., 2004).
Their inclusion also improves the compressive
and flexural strength of concrete.
The sensing capabilities of concrete are in-
valuable not only for real time structural health
monitoring, but also for the construction of smart
structures. This is simply because they do not
invoke the use of embedded or attached sensors.
Kawashima et al., (2013) observed that nano
nanoCaCO3 take part in accelerating heat of
hydration, setting time and upgrading compres-
sive strength of concrete. Sonication improved
the implications of nano-CaCO3 in each scenario.
Nano-TiO2 has been identified as a potential
nanomaterial with wide range applications. This
is mainly because of its strong oxidizing capacity
under U-V radiation, chemical stability, chemical
inertness in absence of U-V light and absence of
toxicity. The photocatalytic Nano-TiO2 is ener-
gized by UV and accelerates the decomposition

Applications of Nanotechnology in Cement and Concrete Science
of organic particulates and airborne pollutants
such as nitrous oxide (NOx) as shown in Figure
7. Studies (Jayapalam et al., 2009) have shown
that nano-TiO2 can accelerate early age hydra-
tion of Portland cement. They are also found to
improve the compressive and flexural strengths of
concrete (Li et al., 2007). The authors also found
that the abrasion resistance of concrete containing
Nano-TiO2 is better than that containing the same
amount of nano-SiO2. Nano-TiO2 has proven to
be very effective to produce self-cleaning and
depolluting concrete (Murata et al., 1999; Val-
lee et al., 2004). Nano-TiO2 based self-cleaning
concrete products are commercially available.
Carbon nanotubes/nanofibres (CNTs/CNFs)
are potential candidates for use as nano rein-
forcements in concrete. CNTs/CNFs exhibit
extraordinary strength with moduli of elasticity
on the order of TPa and tensile strength in the
range of GPa, and they have unique electronic
and chemical properties (Srivastava et al., 2003).
Figure 7. Photocatalytic nano-TiO2 is energized by UV
CNTs/CNFs, thus, appear to be among the most
promising nanomaterials for enhancing the me-
chanical properties of concrete and their resistance
to crack propagation while providing such novel
properties as electromagnetic field shielding and
self-sensing (Makar et al., 2005; Li et al., 2007).
Single-wall CNTs (SWCNTs), multi-wall
CNTs (MWCNTs), and CNFs are highly struc-
tured graphene ring-based materials with very
large aspect ratios (of 1000 or more) and very
high surface areas. SWCNTs are single graphene
cylinders and MWCNTs are multiple, concentric
graphene cylinders coaxially arranged around a
hollow core. Unlike CNTs, CNFs present nu-
merous exposed edge planes along the surface
that constitute potential sites for advantageous
chemical or physical interaction. While CNTs/
CNFs have been extensively studied in polymeric
composites (Hammel et al., 2004; Coleman et al.,
2006; Lau et al., 2006) their use in cement has, to
date, remained limited. One of the main challenges
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