Construction and Building Materials 73 (2014) 113124

Contents lists available at ScienceDirect

Construction and Building Materials

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

Review

Nano reinforced cement and concrete composites and new perspective

from graphene oxide
Samuel Chuah a, Zhu Pan a, Jay G. Sanjayan b, Chien Ming Wang c, Wen Hui Duan a,
a
Department of Civil Engineering, Monash University, Clayton, Victoria 3800, Australia
b
Centre for Sustainable Infrastructure, Faculty of Science Engineering & Technology, Swinburne University of Technology, Hawthorn, Victoria, Australia
c
Engineering Science Programme and Department of Civil and Environmental Engineering, National University of Singapore, Kent Ridge, 119260, Singapore

h i g h l i g h t s

 Summarizing the latest literature on CNTs and GO reinforced cement composites.

 Cement fabrication focuses on separating and avoiding re-agglomeration of nanomaterials.
 Preserving the workability of nanocomposites is accomplished by using admixtures.
 The seeding of CSH gel occurs on the large surface area of nanomaterials.
 Reinforcement and pore renement by 1D and 2D nanomaterials strengthen cement.

a r t i c l e i n f o a b s t r a c t

Article history: Progress in the eld of nanomaterials presents an invaluable opportunity to develop cementitious com-
Received 14 January 2014 posites at the nanoscale. Engineered nanomaterials exist in three principal shapes, namely 0D nanopar-
Received in revised form 6 June 2014 ticle, 1D nanober and 2D nanosheet. The application of 0D nanoparticle and 1D nanober, such as
Accepted 14 September 2014
nanosilica and carbon nanotubes (CNTs), respectively, has been reported in literature. The discovery of
Available online 15 October 2014
2D nanosheet known as graphene oxide (GO) provides an extra dimension to interact with cement and
concrete matrix and has yet to gain widespread attention. In this paper, recent research studies in devel-
Keywords:
oping cement and concrete nanocomposites are comprehensively reviewed. Also highlighted herein are
Graphene oxide
Carbon nanotubes
the effect of incorporating nanomaterials in low dosages to the fabrication, workability, hydration, micro-
Ordinary Portland cement structure, and mechanical properties of cement-based composites.
Dispersion 2014 Elsevier Ltd. All rights reserved.
Fabrication
Hydration
Porosity
Mechanical property

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
2. Physical and chemical properties of common nanofillers for cement and concrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
3. Fabrication of nano cement and concrete composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
3.1. Mechanical methods for dispersion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
3.2. Physical surface modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
3.3. Chemical surface modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
3.4. Preparation of cement composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
4. Workability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
5. Effect of nano fillers on hydration behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
6. Microstructure of nano reinforced cement and concrete composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
7. Mechanical properties of hardened composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120

Corresponding author.
E-mail address: Wenhui.duan@monash.edu (W.H. Duan).

http://dx.doi.org/10.1016/j.conbuildmat.2014.09.040
0950-0618/ 2014 Elsevier Ltd. All rights reserved.
114 S. Chuah et al. / Construction and Building Materials 73 (2014) 113124

7.1. Nanosilica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120

7.2. CNTs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
7.3. CNTs with fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
7.4. Graphene oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
8. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122

1. Introduction
Till this day, ordinary Portland cement (OPC) retains its popu-
larity as the construction material of choice in the eld of civil
engineering. The global production of cement has exceeded 3.6 bil-
lion tonnes in meeting mankinds thirst for urbanization that
involves construction of buildings and infrastructure, especially
in fast developing countries such as China and India [1]. Cement
is the principal binder holding the aggregates together to produce
concrete in the presence of water for hydration. As an engineered
material, concrete composites are desired for their excellent com-
pressive strength.
However, the major disadvantage of concrete is its brittle nat-
ure which is attributed to its poor resistance to crack formation,
low tensile strength and strain capacities. Depending on the mix
proportions of aggregates, cement and water, the tensile strength
of concrete lies in the range of 28 MPa [2]. Many attempts have
been directed at enhancing the performance of cement based
materials by manipulating the properties of cement composites
with admixtures [36], supplementary cementitious materials
[710], and bers [1114]. Fiber Reinforced Concrete (FRC)
research began in earnest since the 1960s. Currently, FRC is com-
monly used for special applications (e.g. shotcreting, slab rein-
forcement, wall cladding, bridge decks, earthquake-resistant
structures and precast concrete) and the research in FRC is still
continuing [15]. FRC provides increased toughness and tensile
strength. In addition, bers replace large cracks with a dense sys-
tem of microcracks but the bers fail to stop crack initiation at
nanoscale. Nanotechnology advancements have provided exciting
opportunities to further raise the performance bar with the inclu-
sion of nanomaterials in cement.
There have been many recent studies on newly produced
nanomaterials such as nanosilica, nanotitanium oxide, nanoiron
oxide, carbon nanotubes (CNTs) and graphene oxide (GO) sheets.
These nanomaterials may be classied according to their shape
or morphology: zero-dimensional (0D) particles, one-dimensional
(1D) bers and two-dimensional (2D) sheets. Nanomaterials are
treasured for their large surface areas that can be exploited for
reaction with cement paste. Although this is benecial as seeding
sites for hydration products, agglomeration of nanomaterials may
arise from the strong van der Waal attractive forces that exist at
the nanoscale. Extra free water is needed to wet the large surface
area of nanomaterials, thereby compromising the cement work-
ability. Nevertheless, the tiny particles are able to ll the pores to
provide a compact microstructure as well as having air purica-
tion, antimicrobial surfaces, and self-cleaning properties to the cur-
rent mundane concrete [16]. Unlike 0D nanoparticles, 1D bers
and 2D sheets behave as reinforcing materials to bridge cracks.
Hence, it is essential for 1D bers and 2D sheets to have high
aspect ratios and intrinsic strength.
Sanchez and Sobolev [17] and Raki et al. [18] documented the
state of the nanotechnology in cement and concrete, especially in
the advancement made in experimental instrumentation and com-
putational simulations as well as nano-engineering and nanomodi-
cation of cement-based materials using a broad range of
nanomaterials. Reviews on nanoparticles have been compiled to dis-
cuss their role in cement composites [19]. Chen et al. [20] summa-
rized the impact of CNTs on cement paste whereas Siddique and
Mehta [21] covered CNT-reinforced mortar.
The current review is concerned with the inuence of the geom-
etry of nanomaterials on the fresh and hardened properties of
cement composites including dispersion, workability, hydration,
microstructure, and mechanical properties. The paper explores
the possibility of implementing two-dimensional sheets in the
form of GO as a new generation of nano-reinforcement. Initial
results on the research of GO in cement composite is shared. At
present, the use of nanomaterials is conned to cement and mortar
matrices, with the long term view for commercial application in
concretes.
2. Physical and chemical properties of common nanollers for
cement and concrete
Over the past years, many reinforcement materials were sys-
tematically investigated for use in FRC [22]. The material proper-
ties of typical llers are summarized in Table 1. They possess
superior elastic modulus and tensile strength when compared to
OPC. Thus, the use of reinforcing material will strengthen concrete
composites in terms of tensile and exural strengths.

Table 1
Material properties of typical llers.

Material Elastic modulus Tensile strength Elongation at Density Diameter/ Surface area Aspect References
(GPa) (GPa) break (%) (kg/m3) thickness (nm) (m2/g) ratio
Graphene 1000 130 0.8 2200 0.08 2600 6000 [28,29]
600,000
GO 2342 0.13 0.6 1800 0.67 7001500 1500 [30,31]
45,000
CNTs 950 1163 12 1330 1540 70400 1000 [32,33]
10,000
Carbon ber 7400 0.45 1.7 1770 600020,000 0.134 1001000 [34,35]
Polymeric ber (Polypropylene 35 0.30.9 18 900 18,00030,000 0.225 1601000 [36,37]
and Nylon)
Glass ber 72 3.45 4.8 2540 500010,000 0.3 6001500 [38,39]
Steel ber 200 1.50 3.2 7800 50,000900,000 0.02 4580 [40,41]
 S. Chuah et al. / Construction and Building Materials 73 (2014) 113124 115

Nano-Engineered Concrete

High Performance Concrete

Graphene Convenonal Concrete
CNTs

Specic Surface Area (m 2/kg)

Graphene
oxide
Nanoparcles Silica fume
Metakaolin
Finely ground OPC
mineral addives Mineral addives
Fly ash
Fine aggregates
Coarse
aggregates

Parcle Size (nm)

Fig. 1. Comparison of nanollers with supplementary cementitious materials and aggregates in concrete. Adapted from Sobolev and Ferrada Gutierrez [49].

Microbers (such as steel, glass, polymeric or carbon) have been
extensively used to reinforce cement and concrete in the past dec-
ades. They have relatively large aspect ratios ranging from 10 to
1000 and their material properties are presented in Table 1. Carbon
ber is commonly used in the construction industry for retrotting
steel and concrete structures [23] owing to its considerable elastic
modulus exceeding 200 MPa and tensile strength of 3.5 GPa. Com-
parable mechanical properties are displayed by steel bers, with
the advantage of controlling the cracks related to expansion caused
by alkali silica reaction and rebar corrosion [24]. The 72.4 GPa elas-
tic modulus and 3.45 MPa tensile strength allow glass bers to
improve the tensile and exural strengths of cement [25]. Achiev-
ing the aforementioned degree of improvement is possible by using
surface treatment and high zirconia glass to resist the strongly alka-
line medium in OPC [26]. Even polypropylene bers with poor
mechanical properties have the ability to strengthen the brittle
cementitious matrix via mechanical anchoring [27].
Fibers strengthen the cement matrix by carrying part of the
applied load and above all, permitting crack and pore-bridging
capabilities [42]. A large aspect ratio and excellent intrinsic
strength of bers are prerequisites for providing reinforcement.
The bridging mechanism supplied by microbers has improved
the tensile strength and toughness. It has been demonstrated that
in lieu of large cracks, microbers will form a dense system of
microcracks but they fail to stop the initiation of cracks. Although
the inclusion of microbers enhances the ductility and toughness,
it does not inuence the compressive strength [43]. Furthermore,
microbers pose problems to the reinforced cement by entrapping
air voids and degrading workability. Functionalization of carbon
and polymer bers can form covalent bonds with cement matrix
but their relatively small surface areas limit the interfacial strength
[44]. In this regard, nanomaterials present a better solution than
traditional bers because the former provides reinforcement or
modication at the nanoscale.
Typical nanollers include nanoparticles, CNTs and GO that
have the potential to improve the strength and durability of con-
cretes. Their sizes are compared with the typical components in
cement and concrete as shown in Fig. 1. In the past, cement powder
was deemed to be the nest component to bind the aggregates to
form conventional concrete. The call for high performance concrete
led to the introduction of supplementary cementitious materials
including y ash, blast furnace slag, metakaolin and silica fume.
With the advancement of nanotechnology, nanomaterials have
been added into cement and concrete. Better performance is antic-
ipated by reinforcing cement matrix at the nanoscale since their
sizes are closer to that of calcium silicate hydrate (CSH) gel [18].
Nanoparticles in powder form such as nanosilica (nano-SiO2),
nano-alumina (nano-Al2O3) and nano-iron (nano-Fe2O3) have been
widely utilized in cement and concrete [45]. Meanwhile, progress is
underway to introduce nano-titanium oxide (nano-TiO2), nano-
clays and calcium carbonate nanoparticles (nano-CaCO3) into the
civil practice [46]. The particle size ranges from 10 to 70 nm as
presented in Fig. 1, enabling lling and reactive characteristics.
Nanoparticles possess pozzolanic characteristics that consume the
non-strength contributing calcium hydroxide (or CH crystals) to
produce CSH. As a result, the orientation and size of CH crystals
are diminished; thereby improving the interface structure [47].
The physical ller effect plays a more prominent role at higher

Fig. 2. (a) Wrinkled graphene [71] and (b) graphene oxide [72].
116 S. Chuah et al. / Construction and Building Materials 73 (2014) 113124
dosage of nanoparticles. For instance, additional nanosilica from 3%
to 6% will continue to rene the pore structure, albeit the consump-
tion of CH stagnates [48].
Within the nanocarbon family, CNTs are 1D carbon allotropes
with a cylindrical nanostructure, that may be viewed as a rolled
up from a single planar sheet of graphene as shown in Fig. 2. Pris-
tine graphene and CNTs exhibit extraordinary elastic modulus
approaching 1 TPa and tensile strength of 1163 GPa. Supplemen-
tary characteristics namely elastic properties [50], excellent ther-
mal properties [51] and electrical conductivity [52] enable
multifunctional and smart attributes. A large aspect ratio surpass-
ing 1000 helps in the physical reinforcement whilst the large
surface area within the vicinity of 1002600 m2/g contributed by
these nano-sized carbon allotropes makes them highly reactive.
These fundamental attributes have vast applications in the eld
of electronics [53], nanoltration [54], biologically-compatible
devices [55,56], and nanocomposites including polymer [57],
ceramic [58] and cement matrices [59]. In the context of reinforc-
ing cementitious composites, these nanocarbons offer substantial
aspect ratios for improving the mechanical properties of brittle
cement as well as promoting the reactivity due to its large surface
area.
As a graphene derivative, GO consists of a hexagonal carbon
network bearing hydroxyl, epoxide, carboxyl and carbonyl func-
tional groups as shown in Fig. 2. These oxygen-containing func-
tional groups render GO sheets hydrophilic and highly
dispersible in water [60]. Two-dimensional GO offers a larger sur-
face area for CSH nucleation than the much-researched CNTs
[6163]. Consequently, the various functional groups coupled with
the large surface area create a highly reactive GO nanomaterial.
However, functionalization may degrade the mechanical proper-
ties of graphene when functional groups are grafted [64]. There-
fore, GO sheets exhibit a lower elastic modulus and tensile
strength than graphene. The mean elastic modulus of 32 GPa and
tensile strength of 130 MPa are still superior to cement.
In summary, the major inuence of nanoparticles is to increase
the hydration rate [65,66] whereas 1D nanober and 2D nanosheet
not only accelerate hydration but also reinforce the cement matrix
from their large aspect ratios [61,67]. The introduction of nanom-
aterials in cement to control cracks at nanoscale deserves attention
[68,69]. Since the spacing between individual nanoreinforcements
is so tiny, they are distributed at a ner scale as compared to
traditional bers. Thus, the properties of nanocomposite can be
tailored at an extremely low content of nanomaterial. Surface
effects instead of bulk properties are responsible for the upgraded
performance and novel functionality of nanocomposites [70]. The
increased surface area of nanomaterials raises its reactivity. These
nanomaterials are intended to interact with cement at the nano-
scopic level, with the average diameter of CSH estimated at
5 nm [18]. Cement derives its strength from the high specic
surface area and consequently, the adhesive property from the
nano-sized CSH.
3. Fabrication of nano cement and concrete composites
Nanomaterials have been identied as the strength and durabil-
ity enhancers of cementitious composites provided that the
nanomaterials are well dispersed. Van der Waals forces hold the
nanomaterials together as clumps due to the large surface area of
the nanomaterial. Defect sites in the form of voids or unreacted
pockets is the consequence of agglomerates [73,74]. The stress
concentrated in this zone will eventually lead to rupture.
There have been considerable attempts to disperse nanoparti-
cles, especially nanosilica. Dispersion of nanosilica is crucial to ful-
ll its function as llers. Otherwise, larger agglomerates tend to
push the surrounding cement particles, creating an increased void
space that is detrimental to the nanosilica/cement composite
strength [75]. By recognizing the importance of dispersion, several
researchers stirred nanosilica particles with some water at a rela-
tively high speed of 120 rpm before adding polycarboxylate super-
plasticiser [76,77]. Another type of water-reducing admixture
known as UNF-5 (one kind of b-naphthalene sulfonic acid and
formaldehyde condensate) is useful for improving both the disper-
sion of nanoparticles in cement and workability of concrete [78].
To counter the evolution of air bubbles, a tributyl phosphate defo-
amer is added while stirring. Youse et al. [79] recommended dis-
persing nanoparticles in lime-saturated water followed by
ultrasonication, prior to mixing with cement.
Parveen et al. [80] presented a literature review of the dispersion
of CNTs in various solutions and polymer matrixes. As a supple-
ment, this paper is devoted to the state-of-art practice for dispers-
ing nanomaterials in cement and concrete. Some recent research
studies are selected and summarized in Tables 2 and 3. Compared
with 0D nanosilica, the dispersion of CNTs proves to be a challenge
due to their large aspect ratios. In order to obtain a reasonable dis-
persion, it is crucial to have the following means or their combina-
tions, i.e. chemical surface modication (functionalization) and
physical means that include physical surface modication (surfac-
tant/polymer wrapping), ultrasonication and mechanical stirring.
3.1. Mechanical methods for dispersion
Uniform dispersion is attainable using various types of mechan-
ical methods, including ultrasonication, ball milling, shear mixing,
calendaring, stirring and extrusion [104]. Among the aforemen-
tioned mechanical methods, ultrasonication has been widely used
to achieve a uniform dispersion in an aqueous solution. The ultra-
sonic probe imparts excitation energy to break up the nanotube
clusters via high local shear [105]. Ultrasonication disentangles
the CNT bundles at the expense of decreased aspect ratios. Metaxa
et al. [95] studied the effect of ultrasonication at energies of 2100,
2800 and 3500 kJ/l on the exural strength of the nanocomposite
and found that 2800 kJ/l offers the optimum performance. Low
ultrasonic energies offer ineffective dispersion whereas high
energy input shortens the embedding ber length. Hence, the
energy input must be controlled to avoid excessively fragmented
nanotubes. The extent of damage caused by ultrasonication relies
on the type of CNTs. Sobolkina et al. [92] applied ultrasonication
to disperse nitrogen-doped CNTs (N-CNTs) or mixed CNTs contain-
ing single-, double- and MWCNTs. After sonication, N-CNTs were
observed as individual broken CNT whereas the mixed CNTs form
a net-like distribution. Unfortunately, ultrasonication facilitates
temporary exfoliation of CNTs and often leads to re-agglomeration
[106]. Hitherto, the combination of ultrasonication and surface
modication of CNTs appears as the most promising method.
3.2. Physical surface modication
Surfactants facilitate dispersion of nanomaterials in water by
lowering the surface energy of CNTs. Many past studies have
focused on surfactant-assisted dispersion of CNTs within aqueous
and organic solutions as well as polymer matrices [107]. Concerns
were raised regarding the potential incompatibility of surfactants
with cement hydration by retarding or preventing hydration,
entrapping substantial air in the paste, or undergoing reactions
with admixtures [91]. Polyacrylic acid is reported to behave as a
plasticizing agent for the cement paste and a dispersing agent for
the CNTs [108]. Collins et al. [91] evaluated the dispersion of CNTs
and consistency of fresh CNTsOPC mixtures by using various
chemical admixtures such as air entraining agent, styrene butadi-
ene rubber, calcium naphthalene sulfonate, naphthalene sulfonic
 S. Chuah et al. / Construction and Building Materials 73 (2014) 113124 117

Table 2
Mix design for CNTs in cement-based composite.

Ref. Matrix CNTs (wt.%) w/c Dispersion method Mixing method

Mechanical Chemical
[81] Paste MWCNT/SWCNT 1% 0.36 Sonication (400 W) for 30 min N.A. N.A.
[82] Mortar FMWCNT* 0.5% 0.45 Sonication for 3 h in basin Water-reducing agent Mix for 8 min in rotary
mixer
[83] Paste FMWCNT 0.045 0.25, 0.3, Sonication for 215 min Polyacrylic acid polymer or Gum Arabic Vacuum mixer
0.15% 0.4 surfactant
[84] Mortar Annealed MWCNT 0.4 Sonication in acetone for 4 h Superplasticizer UNI-EN 196-1
0.5%
[85] Paste MWCNT 0.0480.08% 0.5 Sonication at 19002100 J/mL Surfactant-to-CNT ratio of 4 ASTM C305
[86] Paste MWCNT 0.25% 0.4 Sonication for 4 h in N.A. Mix for 5 min in electric
Polyvinylpyrrolidone mixer
[87] Mortar FMWCNT 0.30.75% 0.48 N.A. Polycarboxylate or melamine Concrete mixer
formaldehyde
[88,89] Paste MWCNT 0.08% 0.3 Sonication at 19002100 J/mL Surfactant-to-CNT ratio of 4 ASTM C305
[90] Paste MWCNT 0.040.2% 0.4 Sonication with 0.46 W/mL ADVA cast 575 Planetary blender
[91] Paste MWCNT 0.52% 0.350.6 Sonication for 12 min 7 types of admixtures Kenwood KNM20 planetary
mixer
[92] Paste N-doped CNTs 0.05, 0.5 Sonication for 120 min SDS or Brij 35 and defoamer N.A.
0.25%
[93] Paste FMWCNT 0.020.09% 0.4 Sonication and centrifugation SDS surfactant N.A.
[94] Paste MWCNT 0.51% 0.4 Sonication for 30 or 240 min N.A. Kitchen mixer
[95] Paste CNT 0.05% 0.5 Sonication at 19002100 J/mL Surfactant-to-CNT ratio of 4 ASTM C305
[96] Paste MWCNT 0.050.15% 0.35 Sonication for 30 min Gum Arabic surfactant N.A.

The unit wt.% is with respect to the weight of cement powder.

*
Notes: FMWCNT: functionalized Multi-walled carbon nanotubes.

Table 3
Mix design for CNTs with other additives in cement-based composite.

Ref. Matrix CNTs (wt.%) w/c Dispersion method Mixing method

Mechanical Chemical
[97] Paste CNT 0.022% 0.365 N.A. Silica fume 10% Mortar mixer
[98] Mortar MWCNT 0.5, 1% 0.5 Sonication for 10 min Fly ash 20% N.A.
[99] Paste MWCNT 0.5, 1% 0.5 Sonication for 1 h N.A. N.A.
[100] Mortar MWCNT 0.0050.1% 0.5 N.A. Nanometakaolin in ammonium chloride solution Dry mixing
[101] Paste MWCNT 0.251% 0.4 Sonication for 90 min in ethanol Hydroxyethyl cellulose and carbon ber 0.25% N.A.
[102] Concrete CNT 0.120.4% 0.2 or 0.37 Sonication for 10 min Polyacrylic Acid (PAA) and ADVA cast 575 Mortar mixer
[103] Mortar MWCNT 0.15, 0.3% 0.25 N.A. Silica fume 1030% Polycarboxylate Standard Hobart mixer

acid derivative, lignosulfonate and aliphatic propylene glycol ether
including ethoxylated alkyl phenol which are not compatible with
CNTs, with the exception of polycarboxylate. Studies done by
Tyson et al. [109] and Abu Al-Rub et al. [110] conrmed that the
commercial high-range polycarboxylate based water-reducing
ADVA Cast 575 admixture lowers the viscosity of cement mix.
The amount of polycarboxylate required to attain a successful dis-
persion of CNTs and satisfactory workability is 0.4 wt.% of cement
powder.
3.3. Chemical surface modication
Chemical functionalization refers to the process of attaching
functional groups onto the CNT surface by covalent linkage. Cova-
lent surface modication improves the hydrophilic behavior of
CNTs while reducing their tendency to form agglomerates. Acid
treatment is required to oxidize CNTs before bonding with carbox-
ylic acid (COOH) or hydroxyl groups (OH). Li et al. [82] found
that carboxylic acid functional group can be attached to the CNT
surface by mixing with sulfuric and nitric acid at a 3:1 volume
ratio. The treated CNTs were uniformly dispersed without any
aggregation detected [111]. Nasibulina et al. [93] carried out the
functionalization using a similar protocol with the exception of
eliminating carboxylated carbonaceous fragments (a by-product
of CNT oxidation). Insertion of carboxyl groups on the CNT surface
can also be done using nitric acid only [87]. A disordered entangle-
ment between the nanotubes with no dened orientation was
observed, indicating a proper bond of the carboxyl groups to the
CNT surface. Sanchez et al. [112] also acknowledged the effective-
ness of surface treatment with 70% nitric acid to facilitate carbon
nanober (CNF) dispersion and interfacial interaction between
CNFs and the cement matrix. However, an inevitable side effect
of the aggressive chemical functionalization is the creation of
defects at the CNT surface, consequently degrading the intrinsic
strength [113].
Owing to the importance of dispersing CNTs, researchers have
advocated a combination of ultrasonication and chemical treat-
ment as listed in Tables 3 and 4. In contrast, GO can be dispersed
without the assistance of surfactants. The morphology of GO is a
sheet of functionalized graphene produced from the oxidation of
graphite based on the modied Hummers method [114] that
involves three steps, i.e. oxidation, purication, and exfoliation.
By oxidation, functional groups containing oxygen are inserted into
graphite to increase the interlayer space and convert graphite into
hydrophilic graphite oxide. In fact, the XRD pattern of GO with var-
ious oxygen contents shows that the interlayer spaces between GO
nanosheets get larger with increasing degree of oxidation. Further-
more, these functional groups supply reactive sites that allow the
development of strong bonds with CSH during nucleation
[115]. Thus, GO can be dispersed without the assistance of surfac-
tants because of the electrostatic repulsion from the functional
groups, rather than just the hydrophilicity of GO [116].
118 S. Chuah et al. / Construction and Building Materials 73 (2014) 113124
Table 4
Fresh properties of nanocomposites.
Ref. Admixture type CNT weight fraction (%)
[123] Superplasticiser: polycarboxylate ether 0.02
[89] Surfactant Short 0.08 Long 0.048
[91] 0.8 wt.% polycarboxylate admixture 0.5 (l/d = 150250)
The purication sequence encompasses ltration, centrifuga-
tion, and followed by dialysis. After oxidation, remnant ions from
acid and oxidizing agents must be removed by ltration so as to
avoid the contaminants from interacting with the cement compo-
nents. Centrifugation eliminates unexfoliated graphite oxide which
is usually present in small amounts. Finally, dialysis is needed to
completely remove residual salts and acids via diffusion through
a semi-permeable membrane. Exfoliation, the process of widening
the interlayer space between GO sheets can be accomplished with
the aid of ultrasonication. The desirable GO size may be obtained
by controlling the degree of sonication. Upon successful separation
of the graphite oxide interlayers, the resulting GO sheets are then
harnessed for cement fabrication.
3.4. Preparation of cement composites
Besides dispersing nanomaterials in aqueous solution, the
nanomaterials must also remain dispersed in cement medium for
effective reinforcement. ASTM C305 is usually quoted as the point
of reference for mixing CNTs with cement in the standard Hobart
mixer as shown in Tables 2 and 3. Nevertheless, the high speed
shear mixer can improve the distribution of GO in cement paste
by high shear energy input [117]. The proposed mixing method
conforms to ASTM C1738-11a pertaining to the standard practice
for high shear mixing of hydraulic cement paste. The mixer speed
is capable of reaching high speeds of up to 12,000 rpm in order to
attain a homogenous distribution of GO sheets in cement paste.
Alternatively, a hand mixer operating at a speed of 2000 rpm for
5 min has been used to mix the cement slurry containing GO [62].
4. Workability
Workability is a key parameter to gauge the ease of transport
and placement of fresh concrete. Regardless of the microber type,
the loss of workability is proportional to the concentration of ber
in concrete. Worse still, the inclusion of nanomaterials in cements
alters the rheological properties of pastes and severely degrades
the workability of mortars and concrete mixtures. The large surface
area of nanomaterials demands more water to wet their surface,
thereby reducing the free water content required for lubrication
at a given water-to-cement ratio (w/c).
The addition of nanosilica into the cement matrix caused a
noticeable reduction in ow spread, improved cohesion and
increased yield stress [118]. Berra et al. [119] suggested adding
water in stages instead of pouring all the water prior to mixing.
Retaining a certain amount of water to be added after a short per-
iod of time helps to minimize the adverse effect of nanosilica on
the workability. Kong, Su [75] examined the inuence of nanosilica
size on the fresh properties of cement paste. Small-sized fumed sil-
ica (510 nm) acts as llers to displace some free water in void
spaces and hence contributes to a workable mix. In contrast, large
agglomerates of precipitated silica (2030 nm) absorb some free
water originally contributing to the uidity of paste. The adverse
workability caused by nanosilica has been acknowledged. There-
fore, the use of other additives such as y ash [120] and superplas-
ticisers [121] were recommended to offset the reduction in uidity.
Early work conducted by Kowald and Trettin [122] discovered
that the ow behavior, or consistency of the paste containing
w/c Result
0.21 Flow table test: workability preserved
0.5 Rheology: CNT raises the viscosity from 0.07 to 0.09 Pa s
0.35 Mini-slump: CNT slightly reduce the diameter by 4.7%
0.5 wt.% MWCNTs was substantially reduced and high pressures
of 125 MPa over a duration of 45 min were necessary for adequate
compaction. The ow characteristics of Ultra High Performance
Concrete (UHPC) fresh paste reinforced with 0.02 wt.% MWCNTs
is judged by measuring the inherent spread diameter on the ow
table [123]. Polycarboxylate ether based superplasticiser emerges
as the ideal candidate to preserve the workability of both cement
paste and mortar matrices, coupled with elevated packing density.
The noncovalent approach based on steric stabilization requires
0.72 wt.% polycarboxylate ether to disperse MWCNTs. Collins
et al. [91] assessed the factors governing the workability of CNT
paste mixtures, namely, w/c, ultrasonication, quantity, CNT aspect
ratio and type of admixture. In the end, ultrasonicated CNTs dis-
persed with polycarboxylate provides highly owable mixtures
and excellent compressive strength albeit having a w/c of 0.35
and requires a relatively high concentration of polycarboxylate
admixture by 0.8 wt.%.
Rheology is a laboratory method used to study the ow and
deformation of a material by relating stress, strain, rate of strain
and time [124]. Besides gaining an insight into the uid behavior
of concrete, rheology has been applied to evaluate the degree of
dispersion of CNT suspensions. Higher viscosity corresponds to
suspensions with large scale agglomerates [125]. Konsta-Gdoutos
et al. [89] recognized the importance of sonication to facilitate
proper dispersion while achieving satisfactory viscosity. Cementi-
tious composite reinforced with MWCNTs (length of 10100 lm;
aspect ratio of 1600) using a surfactant to CNT ratio of 6.25 has a
viscosity of 0.09 Pa s, which is close to plain cement paste with
0.07 Pa s at a low shear stress condition. Some research studies
on the workability of CNT/cement are tabulated in Table 4.
The unique 2D GO sheet being a double-edged sword, promotes
CSH nucleation at the expense of a lower workability [61,62].
The hydrophilic GO has a large surface area to adsorb water mole-
cules present in the mix to its surface. As a result of the lack of free
water, the frictional resistance among the cement particles and the
sheets is increased without ample lubrication. This inter-particle
friction phenomena has been identied as the root cause for exac-
erbated workability [126].
The workability dilemma is addressed in depth with the aid of
the conventional mini-slump test accompanied by the rheological
studies. The mini-slump test shows a 50% reduction in workability
whilst the viscosity test conrms the result [117]. In fact, the vis-
cosity increases with the size of GO, conrming the inuence of
geometry on the workability. The larger sized GO experiences
intermeshing, leading to a higher frictional resistance. Therefore,
the dominant force on workability during the investigation of the
effect of aspect ratio is friction instead of water adsorption.
In an earlier investigation on the workability of GO-reinforced
cement, Pan et al. [62] duly noted the reduction in workability is
about 42% via a mini-slump test with the incorporation of
0.05 wt.% GO. It is deduced that admixtures may be required to
improve the workability of GO cement to compensate for the
decrease of available water in the fresh mix, similar to the case of
nanosilica [118] and CNT cement composite [91]. Further tests
using 0.03 wt.% GO also show a signicant decline in workability
by 34.6% [61]. Moreover, it is emphasized that small amounts of
GO sheets (0.020.05 wt.%) exhibits an even poorer workability
than CNTs. These separate studies infer an inverse correlation
 S. Chuah et al. / Construction and Building Materials 73 (2014) 113124
between the concentration of GO and workability. Despite the
excellent dispersion of GO nanosheets in the cement matrix, poly-
carboxylate remains an indispensable admixture for reducing water
consumption without losing the uidity of the cement paste [63].
5. Effect of nano llers on hydration behavior
Anhydrous cement is composed of four types of minerals
namely alite (C3S), belite (C2S), aluminate (C3A) and ferrite
(C4AF). Upon adding water to cement grains, various chemical
reactions occur simultaneously to give rise to the formation of a
rigid cement paste. The resulting porous multi-phase matrix con-
tains CH with traces of aluminates and unhydrated clinker
embedded into the binding agent, CSH gel. The CH by-product
is responsible for the cement alkalinity. Thus, extra attention
should be paid towards dispersing nanomaterials in a high pH-
value cement medium. Moreover, the heterogeneous nature of
cement contains mostly calcium ions with traces of magnesium,
aluminum, iron, potassium, sodium and sulfur ions. The interac-
tion of nanomaterials with these ions must also be taken into
account.
Generally, the use of nanomaterials such as nanotubes, nano-
bers, nanosilica or nanoclay are capable of accelerating the degree
of hydration [127]. Nanosilica with large amounts of siliceous sur-
face consumes lime quickly especially at early ages. Nanosilica
with a mean particle size of 12 nm has been proven to expedite
the cement hydration when compared with silica fume 150 nm
in diameter [128]. A higher specic surface area or an extra dosage
will shorten the initial setting time of cement pastes. This short-
ened duration could be a result of the accelerated transformation
of CSH surrounding the cement particles to the stable form,
via fast pozzolanic activity. However, the degree of hydration slows
down after 7 days because the quantity of water available for
hydration is adsorbed by the nanosilica [129]. More evidence per-
taining to the role of nanosilica in accelerating hydration at an
early age can be inferred from the reduction in setting time, short-
ened duration to reach the peak heat of hydration and increased
production of CH at early age [118,130].
The results of the effect of CNTs on the cement hydration are
limited. The accelerated rate of hydration is rst noted by Makar
et al. [131] by using Vickers hardness. Early improvements in the
hardness up to 14 days indicate the role of CNT in accelerating
the growth of hydration products via nucleation. Further evidence
of CNTs acting as nucleating sites for C3S hydration products is pre-
sented by Makar and Chan [132] whereby CNTs were rapidly
coated with CSH.
Besides the aforementioned nanomaterials, GO also accelerates
the rate of hydration. The non-evaporable water is measured with
TGA as hydration progresses with time. The test aims to gauge the
degree of hydration by recording the non-evaporable water and CH
content within the cement composite. GO cement increases the
non-evaporable water content by 9% and CH by 6% [61]. This dis-
parity in water and CH contents is consistently at a higher propor-
tion than OPC at all ages. Hence, GO increases the degree of
crystallinity in polymeric nanocomposite by providing preferential
nucleation site at its oxygen functional groups. Lv et al. [63] mon-
itored the development of hydration products periodically under
SEM. They discovered that the functional groups of GO plays a
major role as the growth points of hydration products by attracting
C3S, C2S and C3A.
6. Microstructure of nano reinforced cement and concrete
composites
Analyzing the porosity of nano-reinforced cement is vital since
it is closely related to the mechanical properties. Water sorptivity,
119
nanoindentation and mercury intrusion porosimetry (MIP) are
techniques utilized to quantify the porous nature of cement. Crack
propagation begins at the pores and nanomaterials are instrumen-
tal in rening the pore structure.
Nanosilica accelerates the hydration rate to yield a compact
microstructure at a short curing time [133]. Concrete durability
can be improved with the addition of nanosilica by increasing
resistance to water penetration [134] and mitigating the leaching
of calcium [135]. Moreover, the dense microstructure with mini-
mal amount of CH crystals were reported with the addition of
nanosilica [47]. Thus, renement in microstructure of cement con-
taining nanosilica can be explained not only from the lling effect
of nanosilica but also its participation in the pozzolanic reaction
[76].
Similarly, CNTs densify the cement microstructure by lling the
pores between hydration products of OPC. CNTs reduce the poros-
ity of cement composite by lowering the amount of mesopores,
dened as pore sizes less than 50 nm in diameter [136]. The total
porosity and total surface area diminished with increasing MWCNT
content up to 1 wt.% [99]. The reduced porosity with a uniform
pore size distribution due to CNTs well dispersed with Gum Arabic
is also observed by Wang et al. [96]. The pore renement produces
a compact composite, leading to increased toughness. Thus, it is
more efcient to produce cement matrix with a lower total poros-
ity by dispersing small amounts of CNTs in surfactant. Water sorp-
tivity is employed to characterize the cement porosity through
capillary attraction to gauge the degree of microcracking [137].
Kim et al. [103] used 0.15 wt.% CNTs dispersed with 10% silica fume
subjected to water sorptivity testing and concluded that compres-
sive strength is not only affected by total porosity but also by CNT
dispersion, silica fume addition and interfacial interaction between
CNTs and hydration products.
Nanoindentation tests have been applied to characterize the
nanoporosity and amount of CSH gel. It can be deduced that
CNTs are effective in lling the areas between CSH. Samples
reinforced with CNTs exhibit a lower autogenous shrinkage which
is benecial in relieving capillary stresses [85]. As a result of the
improved early strain capacity, shrinkage and microcracking can
be curbed at an early age.
Cement containing 0.5 wt.% functionalized MWCNTs appears to
have the best pore renement effect [82]. The MIP test shows the
reduction in total porosity and pore sizes exceeding 50 nm by
39% and 45%, respectively. In a separate study, 0.3 wt.% functional-
ized MWCNTs dispersed with two admixtures of naphthalene-sul-
fonate plasticizer and modied polycarboxylate resulted in 21.6%
lower porosity and 31.3% smaller average pore diameter [87].
The prospect of using functionalized CNTs appears promising for
producing highly durable cement. The outcomes of the aforemen-
tioned tests for determining the microstructure of CNT/cement are
listed in Table 5.
GO has a profound impact on the surface area and pore struc-
ture occurring at the nanoscale. The increased surface area corre-
sponds to the development of the highly porous phase. Nitrogen
absorption/desorption technique detected an increase in pore
diameter at nanoscale (180 nm) [62]. The small pores (1
10 nm), also known as gel pores are composed of pore system in
CSH gel. The inference of GO promoting the hydration process
due to the increased proportion of gel pores is postulated.
An alternative method to characterize the porosity of GO-
cement described in a pore size distribution is conducted using
MIP [61]. The results indicate that the inclusion of GO successfully
rened the microstructure by lowering the amount of capillary
pores (between 10 nm and 10 lm) by 27.7%, doubling gel pore vol-
ume by 109%, and reducing the total porosity by 13.5%, which are
closely related to the accelerated hydration owing to the 2D shape
of GO.
120 S. Chuah et al. / Construction and Building Materials 73 (2014) 113124

Table 5
Microstructure results of nanocomposites.

Ref. Methodology Test Amount and Results

CNT type
[82] Sonication and carboxylation with sulfuric and nitric acid MIP 0.5% FCNT Total porosity decreased by 39% Pores with
diameter exceeding 50 nm decreased by 45%
[97] Mixing of CNF, cement, SF followed by water Water/N2 2% CNF and 10% Water porosity decreased by 8% CNF promoted
absorption Silica fume pore renement at 6200 nm diameter range
[85] [89] Ultrasonication and surfactant Nano- 0.08% MWCNT Youngs Modulus <10 GPa corresponding to the
indentation porous phase is reduced
[87] Naphthalene-sulfonate plasticizer and polycarboxylate N2 0.3% FMWCNT Total porosity reduced by 21.6% Mean pore
admixtures absorption diameter reduced by 31.3%
[99] Ultrasonication MIP 1% MWCNT Total porosity decreased by 16% Total surface
area decreased by 22.6%
[92] Ultrasonication and 0.25% wt surfactant and foam reducing MIP 0.05 % N-doped SDS: Highly porous samples caused by formation
agent MWCNT of foam Brij 35: Denser microstructure
[96] Ultrasonication and 0.48% wt Gum Arabic surfactant with MIP 0.12% wt Total porosity reduced by 20.92% Mean pore
0.13% wt tributyl phosphate defoamer MWCNT diameter reduced by 56.2%
[103] Mixing and 1.6% polycarboxylic acid admixture Water 0.15% CNT and Denser microstructure
absorption 10% silica fume

7. Mechanical properties of hardened composites
Nanomaterials such as nanotubes, nanobers, nanosilica or
nanoclay are capable of accelerating the degree of hydration
[127] due to the large total surface area, which has the potential
to improve the mechanical properties. Improvements in mechani-
cal properties especially at an early age are testament to the effec-
tiveness of nanomaterials in contributing to the development of
fracture toughness, compressive, exural and tensile strengths
(see Tables 6 and 7).
liberated CH leaches out to replace a portion of cement. This phe-
nomenon is detrimental to the compressive strength since the
redundant nanosilica (depleted CH) does not contribute to
strength. Furthermore, the size of ller signicantly contributes
to the compressive strength. Small-sized nanosilica (510 nm) out-
performed agglomerated nanosilica (2030 nm) by a factor of two.
The ner nanosilica supplies more ller and fewer weak zones
when compared to the use of agglomerated nanosilica [141].
7.2. CNTs

The implementation of 1D CNTs and 2D GO with an enormous

7.1. Nanosilica
The increased amount of CSH gel is responsible for the
increased compressive and exural strengths when nanosilica is
added into cement [76]. The best mechanical performance of con-
crete containing 4 wt.% nanosilica recorded compressive, tensile
and exural strengths greater than control specimens by a factor
of 1.7, 2.2 and 1.6 times respectively after 28 days. At 5 wt.% addi-
tion of nanosilica, the mechanical properties begin to decrease in
comparison to the optimal dosage of 4 wt.% is primarily due to
the defects generated by inadequate dispersion [140]. The amount
of nanosilica surpassing the quantity required to combine with
surface area is a promising prospect with regard to reinforcing
cement at the nanoscale on top of the nucleating effect displayed
by 0D nanosilica.
Preliminary efforts by Campillo et al. [81] showed that
MWCNTs outperforms SWCNT because the presence of defects
can be advantageous in terms of increasing the interaction points
with the matrix and securing a better anchorage. Functionalized
CNTs supply supercial functional groups, leading to a strong cova-
lent force on the interface between the reinforcement and matrix
as veried by the SEM and FT-IR [82]. Overall, the mechanical
properties of the mortar composite are improved because of the
better load-transfer efciency from cement matrix to CNTs.

Table 6
Hardened properties of cement and concrete composites.

Ref. Methodology CNT weight fraction Results (% improvement) Code

(%)
[81] Ultrasonication 1 Compressive: SWCNT : 6% MWCNT: 30% N.A.
[82] Sonication and carboxylation with sulfuric and nitric acid 0.5 Compressive: 19% Flexural: 25% N.A.
[83] Sonication with Polyacrylic acid 0.045 Compressive: 50% Flexural: 10% N.A.
[84] Sonication with acetone and modied acrylic polymer and 0.5 Compressive: 11% Flexural: 34% UNI-EN 196-1
superplasticisers
[138] Sonication and NaDC surfactant 0.2 Compressive: 29.50% Flexural: 35.45% GB/T1 7671
[85] Sonication and surfactant 0.08 Elastic Modulus: 35% Flexural: 40% N.A.
[89] Sonication and surfactant 0.08 Elastic Modulus: 45% Flexural: 25% ASTM C348
[86] Sonication and polyvinylpyrrolidone organic solvent 0.25 Load capacity: 47% Toughness: 25% N.A.
[87] Naphthalene-sulfonate plasticizer and modied polycarboxylate 0.3 Modulus: 14% Compressive: 12% Splitting NBR 7215, 8522
admixtures tensile: 34% 7222
[88] Sonication, surfactant and swing centrifugation 0.08 Elastic Modulus: 35% Flexural: 35% ASTM C348
[90] Sonication and water reducing admixture ADVA cast 575 0.2 Flexural : 269% Ductility: 81% N.A.
[91] Sonication and polycarboxylate admixture 0.5 Compressive: 25% N.A.
[92] Sonication and surfactant (Brij35 and foam reducing agent) 0.05 Compressive: 40% N.A.
[93] Sonication and puried from carboxylated carbonaceous 0.03 Compressive: 97.2% N.A.
fragments
[94] Sonication 0.5 Compressive: 15% Splitting tensile: 36% ASTM C39 C496
[95] Debulking, sonication and surfactant 0.048 Elastic Modulus: 75% Flexural: 50% N.A.
[96] Sonication and Gum Arabic surfactant with tributyl phosphate 0.08 Flexural toughness index: 57.5% ASTM C1018-97
defoamer
 S. Chuah et al. / Construction and Building Materials 73 (2014) 113124
Table 7
Hardened properties of nanocomposite containing other additives.
Ref. Methodology
[98] Sonication for 10 min
[100] Dry mixing
[101] CNT: sonication in ethanol CF: sonication in hydroxyethyl
cellulose (HEC)
[139] Sonication in acetone, mix cement, CaCl2, bagasse ber and CNT
for cement panel
[102] Sonication with Polyacrylic acid and 4.9% polycarboxylate in
water, microwave radiation to produce UHPC
[103] Mixing and 1.6% Polycarboxylic acid admixture
Cwirzen et al. [83] performed a compressive testing on nano-
composites with 15 different combinations of w/c ratios, MWCNTs
(pristine and functionalized) and surfactant. One of the trial mix
displays an increase in compressive strength by 50% with the addi-
tion of 0.045 wt.%. COOH modied MWCNTs. Musso et al. [84]
claimed that commercially obtained functionalized CNTs are infe-
rior to pristine and annealed CNTs due to the hydrophilic func-
tional groups having the ability to adsorb water while hampering
the hydration process. TGA results showing a lower amount of
tobermorite gel formation was used to support this argument.
Findings made by Makar and Chan [132] supported the fact that
CSH preferred to form on the surface of nanotube bundles rather
than on the surface of adjacent cement grains. The dense CSH
formation appears to be tightly bonded to the CNTs, demonstrating
reinforcing behavior. Konsta-Gdoutos et al. [89] recorded a sub-
stantial increase in Youngs Modulus by 45% and exural strength
by 25% when the MWCNT reinforced sample is subjected to three
point bending. Nanomechanical tests carried out by using nanoin-
dentation suggest that MWCNTs increase the amount of high stiff-
ness CSH while reducing the nanoporosity.
Abu Al-Rub et al. [90] measured the mechanical properties of
CNTOPC composites containing different concentrations and
aspect ratios of MWCNTs. The reinforcing ability provided by nano-
composites with a low concentration of long MWCNTs gives com-
parable mechanical performance to nanocomposites with a higher
concentration of short MWCNTs. Besides economic considerations,
short MWCNTs at high concentrations help to arrest microcracks
better. Furthermore, CNTs with low aspect ratios are more effective
in lling nano-sized voids while enhancing the packing density.
Application of MWCNTs dispersed by Gum Arabic elevates both
the fracture energy and exural toughness of OPC paste [96]. The
observed CNT pull-out without rupture failure ensures the load
transfer in the case of tension and eventually contributes to
improved exural toughness. Moreover, the CNTs acting as bridges
across cracks and voids establish a network to transfer the load in
tension.
7.3. CNTs with llers
Tiny particles can be mixed together with 1D nanoreinforce-
ments for synergetic benets. For example, the reinforcing ability
of CNTs to compensate the strength reduction associated with
the replacement of cement with y ash by 20% [98]. Sanchez and
Ince [97] exploited the ne particle size of SF ranging 100
500 nm to behave as wedges in an attempt to mechanically sepa-
rate the CNFs. By placing the SF between CNFs, the Van der Waals
forces are rendered ineffective. Further work is conducted by Kim
et al. [103] to ne tune the mix proportion of varying contents of
CNTs and SF within the mortar matrix. Mixing 0.15% CNTs with
10% SF gives the best improvement in compressive strength with
121
Mix ratio Results (% improvement) Code
1% CNT with 20% Fly Compressive: 10%
ash
0.02% MWCNT and 6% Compressive: 29% ASTM
NMK C109
0.75% MWCNT and Flexural: 88.42% Load carrying capacity: 366.67% IS 4031
0.25% CF
1.5% MWCNT with Flexural: 43%
20% bagasse ber
0.145% CNF and 3.55% Flexural : 46% Max deection : 2200% Energy ASTM C78,
steel ber sorption : 3400% Impact resistance: 280% D7136
0.15% CNT and 10% Compressive: 32% ASTM C39
silica fume
a 32% increase. SF can mechanically break the agglomerates into
smaller sizes without ultrasonication. Adding more SF was found
to separate agglomerated CNTs better although the degree of
improvement is not as prominent as 10% addition of SF. The addi-
tion of CNTs should not exceed 0.15% otherwise reagglomeration
will occur, leaving an adverse impact on the compressive strength.
The similar concept of using minuscule particles to facilitate
dispersion of CNTs was put to practice by Morsy et al. [100].
Nanometakaolin (NMK) and CNTs have a complementary strength-
ening effect on the cement nano-composite in terms of dispersion,
packing effect and pozzolanic reaction and resisting microcracks.
Utilizing 6 wt.% exfoliated NMK, various CNT ratios were tested
and the optimum amount is found to be 0.02 wt.% MWCNTs. In
fact, the enhanced compressive strength of 29% and 18% compared
to cement mortar and 6 wt.% NMK with cement mortar, respec-
tively, is proof of higher performance by hybrid reinforcement.
Recently, Peyvandi et al. [102] combined steel microbers with
CNFs to control the inception and growth of cracks encompassing
all scales. Dispersed using polyacrylic acid in water for sonication
and followed by polycarboxylate to produce UHPC, the nanobers
enhance the bonding and pullout behavior of microbers. The 46%
increase in exure is related to the toughening effects from pulling
out the bers. The UHPC matrix also offers higher compaction den-
sity, reduced porosity, ner capillary pore system together with
improved interfacial bonding as compared to normal cement
matrix.
7.4. Graphene oxide
The unique features of the two-dimensional GO such as its
rough surface and functional group have a favorable inuence on
the mechanical behavior of cement. Introducing small quantities
of GO as little as 0.05 wt.% increases the compressive strength by
1533% and the exural strength by 4159%, respectively [62].
The compressive and exural strengths of GO-cement outperform
its plain cement counterpart encompassing all ages till 56 days.
In addition, the small standard deviation in strength highlights that
GO has little inuence on strength anisotropy. The astounding
enhancement is accredited to the very large surface area offered
by the 2D GO sheet.
Reinforcing cement with GO is benecial in terms of its superior
aspect ratio when compared to conventional bers as illustrated in
Table 1. Reaction wise, GO has a seeding effect on the cement
hydration kinetics, stimulating the growth of hydration products.
Initial studies on the failure mode show that the GO-reinforced
cement exhibits ductile behavior. The interfacial adhesion by
GOs functional groups corresponds to the case of functionalized
CNTs [82]. The strong covalent bond on the GO interface with
hydration products deposited on the sheet makes GO a promising
material to enhance the cement matrix.
122 S. Chuah et al. / Construction and Building Materials 73 (2014) 113124
Fig. 3. Effect of 0.05 wt.% GO for w/c of 0.5 on: (a) Stressstrain curves under compression; (b) Loaddisplacement curves under exure [62].
The elastic modulus gathered from the stressstrain curve
depicted in Fig. 3 shows a moderate increase to 3.7 MPa from
3.48 MPa. The increased strain capacity can be explained from
the delayed microcrack initiation. In a separate investigation of
the effect of 0.03 wt.% of GO, the compressive strength improved
by 46.2% alongside increased failure stress and strain [61]. GO
shows a better gain in compressive strength at a lower concentra-
tion when compared to CNT reinforced cement. The gain is attrib-
uted to the excellent reinforcement provided by GO.
8. Concluding remarks
The impact of nanomaterials in the form of 0D particles, 1D
bers and 2D sheets on cement and concrete composites have been
reviewed. Reports dating back from the turn of the 21st century
have presented the advantages of nanomaterials. The effects of
nanomaterials on the cement and concrete can be summarized as
follows:
 Careful attention should be dedicated to the mixing of nanoma-
terial slurry as well as the quality of nanomaterials such as
nanosilica, CNTs and GO to name a few. Agglomeration of
nanomaterials is a common problem due to the strong van
der Waals attractive forces at the nanoscale. Obtaining properly
dispersed nanomaterial requires a combination of sonication for
mechanical separation and admixture to avoid re-agglomera-
tion in the cement matrix.
 Inclusion of nanomaterial often degrades the workability of
cement pastes, which may be attributed to the adsorption of
free water onto the surface of nanomaterials. The use of com-
patible admixture is one of the feasible ways for addressing this
issue. Nanomaterials are highly reactive and could accelerate
the hydration of cement by providing attachment sites for the
CSH gel. The seeding of CSH gel onto the large surface of
the nanomaterials is the major incentive for using them.
 Pore renement by nanomaterials is highly desirable since it
contributes to durability and strength. Reinforcement by 1D
nanober and 2D nanosheet are responsible for the crack bridg-
ing behavior for strengthening cement. Improvements in frac-
ture toughness, compressive, exural and tensile strengths
due to the addition of nanomaterials are consistently reported
in literature.
 Among all the mentioned nanollers, GO appears to be an ideal
candidate to enhance the properties of cement-based compos-
ite. The excellent intrinsic properties of the 2D nanosheet can
strengthen the brittle cement matrix, similar to CNTs. Further-
more, the oxygen-bearing functional groups are desirable for
homogeneous dispersion in cement, nucleation of CSH and
densify the microstructure.
To fulll the promise of newly developed nanomaterials in the
construction industry, the following issues should be addressed.
 Agglomeration of nanomaterials hinders their potential to
improve the properties of concrete. In this regard, the disper-
sion mechanism of nanomaterials is yet to be developed.
Although GO appears to be well-dispersed in water, there is
no such guarantee of good dispersion in the cement matrix.
 Admixtures play an important role to preserve the cement
workability when nanomaterials are added. However, detailed
studies on the role of nanomaterials on the hydration and inter-
action with the various phases of cement, including admixtures
require attention.
 The durability aspect of cement and mortar containing nanoma-
terial provides an interesting avenue for research. The behavior
of such composite under degradation such as decarbonation,
acid resistance, sulfate resistance should be analyzed.
 More in-depth studies are needed to prove the role of nanoma-
terials as nucleating sites with the aid of nanoscale instrumen-
tation as well as the atomistic modeling.
Acknowledgments
The authors gratefully acknowledge the nancial support from
the Australian Research Council Australia in conducting this
study.
References
[1] Zhang T et al. Effectiveness of novel and traditional methods to incorporate
industrial wastes in cementitious materials an overview. Resour Conserv
Recycling 2013;74:13443.
[2] Neville AM, Brooks JJ. Concrete technology. Prentice Hall/Pearson; 2010.
[3] Hanehara S, Yamada K. Interaction between cement and chemical admixture
from the point of cement hydration, absorption behaviour of admixture, and
paste rheology. Cem Concr Res 1999;29(8):115965.
[4] Jae Hong K, Beacraft M, Shah SP. Effect of mineral admixtures on formwork
pressure of self-consolidating concrete. Cem Concr Compos 2010;32(9):
66571.
[5] Zhang M-H et al. Effect of superplasticizers on workability retention and
initial setting time of cement pastes. Constr Build Mater 2010;24(9):17007.
[6] Cheung J et al. Impact of admixtures on the hydration kinetics of Portland
cement. Cem Concr Res 2011;41(12):1289309.
[7] Lothenbach B, Scrivener K, Hooton RD. Supplementary cementitious
materials. Cem Concr Res 2011;41(3):21729.
[8] Sobolev K. Mechano-chemical modication of cement with high volumes of
blast furnace slag. Cem Concr Compos 2005;27(78):84853.
[9] Shi C, Qian J. High performance cementing materials from industrial slags a
review. Resour Conserv Recycling 2000;29(3):195207.
[10] Sahmaran M, Christianto HA, Yaman IO. The effect of chemical admixtures
and mineral additives on the properties of self-compacting mortars. Cem
Concr Compos 2006;28(5):43240.
[11] Shah SP, Chengsheng O. Mechanical behavior of ber-reinforced cement-
based composites. J Am Ceram Soc 1991;74(11):272738.
 S. Chuah et al. / Construction and Building Materials 73 (2014) 113124
[12] Wang J-Y, Banthia N, Zhang M-H. Effect of shrinkage reducing admixture on
exural behaviors of ber reinforced cementitious composites. Cem Concr
Compos 2012;34(4):44350.
[13] Juarez C et al. The diagonal tension behavior of ber reinforced concrete
beams. Cem Concr Compos 2007;29(5):4028.
[14] Topcu IB, Canbaz M. Effect of different bers on the mechanical properties of
concrete containing y ash. Constr Build Mater 2007;21(7):148691.
[15] Zollo RF. Fiber-reinforced concrete: an overview after 30 years of
development. Cem Concr Compos 1997;19(2):10722.
[16] Pacheco-Torgal F, Jalali S. Nanotechnology: advantages and drawbacks in the
eld of construction and building materials. Constr Build Mater
2011;25(2):58290.
[17] Sanchez F, Sobolev K. Nanotechnology in concrete a review. Constr Build
Mater 2010;24(11):206071.
[18] Raki L et al. Cement and concrete nanoscience and nanotechnology. Materials
2010;3(2):91842.
[19] Pacheco-Torgal F et al. Targeting HPC with the help of nanoparticles: an
overview. Constr Build Mater 2013;38:36570.
[20] Chen SJ et al. Carbon nanotube-cement composites: a retrospect. IES J Part A:
Civil Struct Eng 2011;4(4):25465.
[21] Siddique R, Mehta A. Effect of carbon nanotubes on properties of cement
mortars. Constr Build Mater 2014;50:11629.
[22] Brandt AM. Fibre reinforced cement-based (FRC) composites after over
40 years of development in building and civil engineering. Compos Struct
2008;86(13):39.
[23] Zhao X-L, Zhang L. State-of-the-art review on FRP strengthened steel
structures. Eng Struct 2007;29(8):180823.
[24] Grubb J et al. Effect of steel microbers on corrosion of steel reinforcing bars.
Cem Concr Res 2007;37(7):111526.
[25] Marikunte S, Aldea C, Shah SP. Durability of glass ber reinforced cement
composites. Adv Cem Based Mater 1997;5(34):1008.
[26] Proctor B, Oakley D, Litherland K. Developments in the assessment and
performance of GRC over 10 years. Composites 1982;13(2):1739.
[27] Bentur A, Peled A, Yankelevsky D. Enhanced bonding of low modulus polymer
bers-cement matrix by means of crimped geometry. Cem Concr Res
1997;27(7):1099111.
[28] Lee C et al. Measurement of the elastic properties and intrinsic strength of
monolayer graphene. Science 2008;321(5887):3858.
[29] Stankovich S et al. Graphene-based composite materials. Nature
2006;442(7100):2826.
[30] Zhu Y et al. Graphene and graphene oxide: synthesis, properties, and
applications. Adv Mater 2010;22(35):390624.
[31] Dikin DA et al. Preparation and characterization of graphene oxide paper.
Nature 2007;448:45760.
[32] Yu M-F et al. Strength and breaking mechanism of multiwalled carbon
nanotubes under tensile load. Science 2000;287(5453):63740.
[33] Peigney A et al. Specic surface area of carbon nanotubes and bundles of
carbon nanotubes. Carbon 2001;39(4):50714.
[34] Li VC, Obla KH. Effect of ber length variation on tensile properties of carbon-
ber cement composites. Compos Eng 1994;4(9):94764.
[35] Banthia N, Djeridane S, Pigeon M. Electrical resistivity of carbon and steel
micro-ber reinforced cements. Cem Concr Res 1992;22(5):80414.
[36] Wang Y, Li VC, Backer S. Tensile properties of synthetic ber reinforced
mortar. Cem Concr Compos 1990;12(1):2940.
[37] Pelisser F et al. Effect of the addition of synthetic bers to concrete thin slabs
on plastic shrinkage cracking. Constr Build Mater 2010;24(11):21716.
[38] Benmokrane B, Chaallal O, Masmoudi R. Glass bre reinforced plastic (GFRP)
rebars for concrete structures. Constr Build Mater 1995;9(6):35364.
[39] Trens P, Denoyel R, Guilloteau E. Evolution of surface composition, porosity,
and surface area of glass bers in a moist atmosphere. Langmuir
1996;12(5):124550.
[40] Yao W, Li J, Wu K. Mechanical properties of hybrid ber-reinforced concrete
at low ber volume fraction. Cem Concr Res 2003;33(1):2730.
[41] Yazici S, Inan G, Tabak V. Effect of aspect ratio and volume fraction of steel
ber on the mechanical properties of SFRC. Constr Build Mater
2007;21(6):12503.
[42] Qian CX, Stroeven P. Development of hybrid polypropylene-steel bre-
reinforced concrete. Cem Concr Res 2000;30(1):639.
[43] Hamoush S, Abu-Lebdeh T, Cummins T. Deection behavior of concrete
beams reinforced with PVA micro-bers. Constr Build Mater
2010;24(11):228593.
[44] Wichmann MHG, Schulte K, Wagner HD. On nanocomposite toughness.
Compos Sci Technol 2008;68(1):32931.
[45] Oltulu M, Sahin R. Effect of nano-SiO2, nano-Al2O3 and nano-Fe2O3 powders
on compressive strengths and capillary water absorption of cement mortar
containing y ash: a comparative study. Energy Build 2013;58:292301.
[46] Kawashima S et al. Modication of cement-based materials with
nanoparticles. Cem Concr Compos 2013;36:815.
[47] Ye Q et al. Inuence of nano-SiO2 addition on properties of hardened cement
paste as compared with silica fume. Constr Build Mater 2007;21(3):53945.
[48] Said AM et al. Properties of concrete incorporating nano-silica. Constr Build
Mater 2012;36:83844.
[49] Sobolev K, Gutierrez MF. How nanotechnology can change the concrete
world. Am Ceram Soc Bull 2005;84(11):169.
[50] Walters DA et al. Elastic strain of freely suspended single-wall carbon
nanotube ropes. Appl Phys Lett 1999;74(25):38035.
123
[51] See CH, Harris AT. A review of carbon nanotube synthesis via uidized-bed
chemical vapor deposition. Ind Eng Chem Res 2007;46(4):9971012.
[52] Kaneto K et al. Electrical conductivities of multi-wall carbon nano tubes.
Synth Metals 1999;103(13 pt 3):25436.
[53] Yang X et al. Bioinspired effective prevention of restacking in multilayered
graphene lms: towards the next generation of high-performance
supercapacitors. Adv Mater 2011;23(25):28338.
[54] Qiu L et al. Controllable corrugation of chemically converted graphene sheets
in water and potential application for nanoltration. Chem Commun
2011;47(20):58102.
[55] Patil AJ et al. Aqueous stabilization and self-assembly of craphene sheets into
layered bio-nanocomposites using DNA. Adv Mater 2009;21(31):315964.
[56] Labroo P, Cui Y. Flexible graphene bio-nanosensor for lactate. Biosens
Bioelectron 2013;41(1):8526.
[57] Kim H, Abdala AA, MacOsko CW. Graphene/polymer nanocomposites.
Macromolecules 2010;43(16):651530.
[58] Tapaszto O et al. Dispersion patterns of graphene and carbon nanotubes in
ceramic matrix composites. Chem Phys Lett 2011;511(46):3403.
[59] Nasibulin AG et al. A novel approach to composite preparation by direct
synthesis of carbon nanomaterial on matrix or ller particles. Acta Mater
2013;61(6):186271.
[60] Qiu L et al. Dispersing carbon nanotubes with graphene oxide in water and
synergistic effects between graphene derivatives. Chem Eur J
2010;16(35):106538.
[61] Gong K et al. Reinforcing effects of graphene oxide on portland cement paste.
J Mater Civil Eng 2014. A4014010.
[62] Pan Z, et al., Graphene oxide reinforced cement and concrete. 2012, WO
Patent App. PCT/AU2012/001,582.
[63] Lv S et al. Effect of graphene oxide nanosheets of microstructure and
mechanical properties of cement composites. Constr Build Mater
2013;49:1217.
[64] Garg A, Sinnott SB. Effect of chemical functionalization on the mechanical
properties of carbon nanotubes. Chem Phys Lett 1998;295(4):2738.
[65] Hou P et al. Modication effects of colloidal nanoSiO2 on cement hydration
and its gel property. Compos Part B: Eng 2013;45(1):4408.
[66] Zhang M-H, Islam J, Peethamparan S. Use of nano-silica to increase early
strength and reduce setting time of concretes with high volumes of slag. Cem
Concr Compos 2012;34(5):65062.
[67] Makar J. The effect of SWCNT and other nanomaterials on cement hydration
and reinforcement in nanotechnology in civil infrastructure. Springer; 2011.
p. 103130.
[68] Makar J, Beaudoin J. Carbon nanotubes and their application in the
construction industry. Special Pub-R Soc Chem 2004;292:33142.
[69] Peyvandi A et al. Surface-modied graphite nanomaterials for improved
reinforcement efciency in cementitious paste. Carbon 2013;63:17586.
[70] Pettitt ME, Lead JR. Minimum physicochemical characterisation requirements
for nanomaterial regulation. Environ Int 2013;52:4150.
[71] Duan WH, Gong K, Wang Q. Controlling the formation of wrinkles in a single
layer graphene sheet subjected to in-plane shear. Carbon 2011;49(9):310712.
[72] Bagri A et al. Structural evolution during the reduction of chemically derived
graphene oxide. Nat Chem 2010;2(7):5817.
[73] Li H et al. Microstructure of cement mortar with nano-particles. Compos Part
B: Eng 2004;35(2):1859.
[74] Hosseinpourpia R et al. Production of waste bio-ber cement-based
composites reinforced with nano-SiO2 particles as a substitute for asbestos
cement composites. Constr Build Mater 2012;31:10511.
[75] Kong D et al. Inuence of nano-silica agglomeration on fresh properties of
cement pastes. Constr Build Mater 2013;43:55762.
[76] Jo B-W et al. Characteristics of cement mortar with nano-SiO2 particles.
Constr Build Mater 2007;21(6):13515.
[77] Najigivi A et al. Investigating the effects of using different types of SiO2
nanoparticles on the mechanical properties of binary blended concrete.
Compos Part B: Eng 2013;54(1):528.
[78] Mao-hua Z, Hui L. Pore structure and chloride permeability of concrete
containing nano-particles for pavement. Constr Build Mater
2011;25(2):60816.
[79] Youse A, Allahverdi A, Hejazi P. Effective dispersion of nano-TiO2 powder for
enhancement of photocatalytic properties in cement mixes. Constr Build
Mater 2013;41:22430.
[80] Parveen S, Rana S, Fangueiro R. A review on nanomaterial dispersion,
microstructure, and mechanical properties of carbon nanotube and nanober
reinforced cementitious composites. J Nanomater 2013;710175:19.
[81] Campillo I, Dolado J, Porro A. High-performance nanostructured materials for
construction. Special Pub-R Soc Chem 2004;292:21526.
[82] Li GY, Wang PM, Zhao X. Mechanical behavior and microstructure of cement
composites incorporating surface-treated multi-walled carbon nanotubes.
Carbon 2005;43(6):123945.
[83] Cwirzen A, Habermehl-Cwirzen K, Penttala V. Surface decoration of carbon
nanotubes and mechanical properties of cement/carbon nanotube
composites. Adv Cem Res 2008;20(2):6573.
[84] Musso S et al. Inuence of carbon nanotubes structure on the mechanical
behavior of cement composites. Compos Sci Technol 2009;69(11
12):198590.
[85] Konsta-Gdoutos MS, Metaxa ZS, Shah SP. Multi-scale mechanical and fracture
characteristics and early-age strain capacity of high performance carbon
nanotube/cement nanocomposites. Cem Concr Compos 2010;32(2):1105.
124 S. Chuah et al. / Construction and Building Materials 73 (2014) 113124
[86] Chan LY, Andrawes B. Finite element analysis of carbon nanotube/cement
composite with degraded bond strength. Comput Mater Sci
2010;47(4):9941004.
[87] Melo VS et al. Macro- and micro-characterization of mortars produced with
carbon nanotubes. ACI Mater J 2011;108(3):32732.
[88] Metaxa ZS et al. Highly concentrated carbon nanotube admixture for nano-
ber reinforced cementitious materials. Cem Concr Compos
2012;34(5):6127.
[89] Konsta-Gdoutos MS, Metaxa ZS, Shah SP. Highly dispersed carbon nanotube
reinforced cement based materials. Cem Concr Res 2010;40(7):10529.
[90] Abu Al-Rub RK, Ashour AI, Tyson BM. On the aspect ratio effect of multi-
walled carbon nanotube reinforcements on the mechanical properties of
cementitious nanocomposites. Constr Build Mater 2012;35:64755.
[91] Collins F, Lambert J, Duan WH. The inuences of admixtures on the
dispersion, workability, and strength of carbon nanotube-OPC paste
mixtures. Cem Concr Compos 2012;34(2):2017.
[92] Sobolkina A et al. Dispersion of carbon nanotubes and its inuence on the
mechanical properties of the cement matrix. Cem Concr Compos
2012;34(10):110413.
[93] Nasibulina LI et al. Effect of carbon nanotube aqueous dispersion quality on
mechanical properties of cement composite. J Nanomater 2012;2012.
[94] Kumar S et al. Effect of multiwalled carbon nanotubes on mechanical strength
of cement paste. J Mater Civil Eng 2011;24(1):8491.
[95] Metaxa ZS, Konsta-Gdoutos MS, Shah SP. Carbon nanober cementitious
composites: effect of debulking procedure on dispersion and reinforcing
efciency. Cem Concr Compos 2013;36:2532.
[96] Wang B, Han Y, Liu S. Effect of highly dispersed carbon nanotubes on the
exural toughness of cement-based composites. Constr Build Mater
2013;46:812.
[97] Sanchez F, Ince C. Microstructure and macroscopic properties of hybrid
carbon nanober/silica fume cement composites. Compos Sci Technol
2009;69(78):13108.
[98] Chaipanich A et al. Compressive strength and microstructure of carbon
nanotubes-y ash cement composites. Mater Sci Eng A 2010;527(4
5):10637.
[99] Nochaiya T, Chaipanich A. Behavior of multi-walled carbon nanotubes on the
porosity and microstructure of cement-based materials. Appl Surf Sci
2011;257(6):19415.
[100] Morsy MS, Alsayed SH, Aqel M. Hybrid effect of carbon nanotube and nano-
clay on physico-mechanical properties of cement mortar. Constr Build Mater
2011;25(1):1459.
[101] Hunashyal A et al. Experimental investigation of the effect of carbon
nanotubes and carbon bres on the behaviour of plain cement composite
beams. IES J Part A: Civil Struct Eng 2011;4(1):2936.
[102] Peyvandi A et al. Effect of the cementitious paste density on the performance
efciency of carbon nanober in concrete nanocomposite. Constr Build Mater
2013;48:2659.
[103] Kim HK, Nam IW, Lee HK. Enhanced effect of carbon nanotube on mechanical
and electrical properties of cement composites by incorporation of silica
fume. Compos Struct 2014;107:609.
[104] Peng-Cheng M et al. Dispersion and functionalization of carbon nanotubes for
polymer-based nanocomposites: a review. Compos Part A: Appl Sci Manuf
2010;41(10):134567.
[105] Strano MS et al. The role of surfactant adsorption during ultrasonication in
the dispersion of single-walled carbon nanotubes. J Nanosci Nanotechnol
2003;3(12):816.
[106] Szleifer I, Yerushalmi-Rozen R. Polymers and carbon nanotubes
dimensionality, interactions and nanotechnology. Polymer
2005;46(19):780318.
[107] Wang H. Dispersing carbon nanotubes using surfactants. Curr Opin Colloid
Interf Sci 2009;14(5):36471.
[108] Cwirzen A et al. SEM/AFM studies of cementitious binder modied by
MWCNT and nano-sized Fe needles. Mater Characterization
2009;60(7):73540.
[109] Tyson BM et al. Carbon nanotubes and carbon nanobers for enhancing the
mechanical properties of nanocomposite cementitious materials. J Mater
Civil Eng 2011;23(7):102835.
[110] Abu Al-Rub RK et al. Mechanical properties of nanocomposite cement
incorporating surface-treated and untreated carbon nanotubes and carbon
nanobers. J Nanomech Micromech 2012;2(1):16.
[111] Li GY, Wang PM, Zhao X. Pressure-sensitive properties and microstructure of
carbon nanotube reinforced cement composites. Cem Concr Compos
2007;29(5):37782.
[112] Sanchez F, Zhang L, Ince C. Multi-scale performance and durability of carbon
nanober/cement composites, in nanotechnology in construction, vol.
3. Springer; 2009. p. 345-350.
[113] Hilding J et al. Dispersion of carbon nanotubes in liquids. J Disper Sci Technol
2003;24(1):141.
[114] Li D et al. Processable aqueous dispersions of graphene nanosheets. Nat
Nanotechnol 2008;3(2):1015.
[115] Lv S et al. Regulation of go on cement hydration crystals and its toughening
effect. Mag Concr Res 2013;65(20):124654.
[116] Geng Y, Wang SJ, Kim J-K. Preparation of graphite nanoplatelets and graphene
sheets. J Colloid Interf Sci 2009;336(2):5928.
[117] Gong K, Tan T, Dowman M, Qiu L, Li D, Collins FG, Duan W. Rheological
behaviours of graphene oxide reinforced cement composite. In: Proceedings
of the 6th international composites conference (ACUN-6): composites &
nanocomposites in civil, offshore and mining infrastructure. 2012. Monash
University, Melbourne, Victoria, Australia.
[118] Senff L et al. Effect of nano-silica on rheology and fresh properties of cement
pastes and mortars. Constr Build Mater 2009;23(7):248791.
[119] Berra M et al. Effects of nanosilica addition on workability and compressive
strength of Portland cement pastes. Constr Build Mater 2012;35:66675.
[120] Hou P et al. Effects of colloidal nanoSiO2 on y ash hydration. Cem Concr
Compos 2012;34(10):1095103.
[121] Senff L et al. Effect of nano-SiO2 and nano-TiO2 addition on the rheological
behavior and the hardened properties of cement mortars. Mater Sci Eng A
2012;532:35461.
[122] Kowald T, Trettin R. Inuence of surface-modied carbon nanotubes on
ultrahigh performance concrete. In: Proceedings of the international
symposium on ultra high performance Concrete; 2004.
[123] Wille K, Loh KJ. Nanoengineering ultra-high-performance concrete with
multiwalled carbon nanotubes. Transport Res Rec 2010;2142:11926.
[124] Banll P. Use of the ViscoCorder to study the rheology of fresh mortar. Mag
Concr Res 1990;42(153):21321.
[125] Ying Y et al. Thermal and rheological properties of carbon nanotube-in-oil
dispersions. J Appl Phys 2006;99(11):114307.
[126] Swamy R. The technology of steel bre reinforced concrete for practical
applications. In: ICE Proceedings; 1994. Ice Virtual Library.
[127] Vera-Agullo J et al. , Mortar and concrete reinforced with nanomaterials, in
nanotechnology in construction, vol. 3. Springer; 2009. p. 383388.
[128] Zhang M-H, Islam J. Use of nano-silica to reduce setting time and increase
early strength of concretes with high volumes of y ash or slag. Constr Build
Mater 2012;29:57380.
[129] Madani H, Bagheri A, Parhizkar T. The pozzolanic reactivity of monodispersed
nanosilica hydrosols and their inuence on the hydration characteristics of
Portland cement. Cem Concr Res 2012;42(12):156370.
[130] Bjrnstrm J et al. Accelerating effects of colloidal nano-silica for benecial
calciumsilicatehydrate formation in cement. Chem Phys Lett
2004;392(1):2428.
[131] Makar J, Margeson J, Luh J. Carbon nanotube/cement compositesearly
results and potential applications. In: Proceedings of the 3rd international
conference on construction materials: performance, innovations and
structural implications, Vancouver, Canada; 2005.
[132] Makar JM, Chan GW. Growth of cement hydration products on single-walled
carbon nanotubes. J Am Ceram Soc 2009;92(6):130310.
[133] Li G. Properties of high-volume y ash concrete incorporating nano-SiO2.
Cem Concr Res 2004;34(6):10439.
[134] Ji T. Preliminary study on the water permeability and microstructure of
concrete incorporating nano-SiO2. Cem Concr Res 2005;35(10):19437.
[135] Gaitero JJ, Campillo I, Guerrero A. Reduction of the calcium leaching rate of
cement paste by addition of silica nanoparticles. Cem Concr Res 2008;38(8
9):11128.
[136] Zdravkov BD et al. Pore classication in the characterization of porous
materials: a perspective. Cent Eur J Chem 2007;5(2):38595.
[137] Collins F, Sanjayan JG. Microcracking and strength development of alkali
activated slag concrete. Cem Concr Compos 2001;23(45):34552.
[138] Luo J, Duan Z, Li H. The inuence of surfactants on the processing of multi-
walled carbon nanotubes in reinforced cement matrix composites. Phys
Status Solidi (A) Appl Mater Sci 2009;206(12):278390.
[139] Kordkheili HY, Hiziroglu S, Farsi M. Some of the physical and mechanical
properties of cement composites manufactured from carbon nanotubes and
bagasse ber. Mater Des 2012;33:3958.
[140] Nazari A, Riahi S. The effects of SiO2 nanoparticles on physical and
mechanical properties of high strength compacting concrete. Compos Part
B: Eng 2011;42(3):5708.
[141] Kong D et al. Inuence of nano-silica agglomeration on microstructure and
properties of the hardened cement-based materials. Constr Build Mater
2012;37:70715.