materials

Review
Recent Progress in Nanomaterials for Modern
Concrete Infrastructure: Advantages and Challenges
Karla P. Bautista-Gutierrez 1 , Agustín L. Herrera-May 1,2, * , Jesús M. Santamaría-López 1 ,
Antonio Honorato-Moreno 1 and Sergio A. Zamora-Castro 1, *
1 Maestría en Ingeniería Aplicada, Facultad de Ingeniería de la Construcción y el Hábitat,
Universidad Veracruzana, Calzada Ruiz Cortines 455, Boca del Río, Veracruz 94294, Mexico;
[email protected] (K.P.B.-G.); [email protected] (J.M.S.-L.);
[email protected] (A.H.-M.)
2 Micro and Nanotechnology Research Center, Universidad Veracruzana, Calzada Ruiz Cortines 455,
Boca del Río, Veracruz 94294, Mexico
* Correspondence: [email protected] (A.L.H.-M.); [email protected] (S.A.Z.-C.);
Tel.: +55-442-226-6337 (A.L.H.-M.)




Received: 23 August 2019; Accepted: 23 October 2019; Published: 29 October 2019


Abstract: Modern concrete infrastructure requires structural components with higher mechanical
strength and greater durability. A solution is the addition of nanomaterials to cement-based materials,
which can enhance their mechanical properties. Some such nanomaterials include nano-silica
(nano-SiO2 ), nano-alumina (nano-Al2 O3 ), nano-ferric oxide (nano-Fe2 O3 ), nano-titanium oxide
(nano-TiO2 ), carbon nanotubes (CNTs), graphene and graphene oxide. These nanomaterials can
be added to cement with other reinforcement materials such as steel fibers, glass, rice hull powder
and fly ash. Optimal dosages of these materials can improve the compressive, tensile and flexural
strength of cement-based materials, as well as their water absorption and workability. The use of these
nanomaterials can enhance the performance and life cycle of concrete infrastructures. This review
presents recent researches about the main effects on performance of cement-based composites caused
by the incorporation of nanomaterials. The nanomaterials could decrease the cement porosity,
generating a denser interfacial transition zone. In addition, nanomaterials reinforced cement can
allow the construction of high-strength concrete structures with greater durability, which will decrease
the maintenance requirements or early replacement. Also, the incorporation of nano-TiO2 and CNTs
in cementitious matrices can provide concrete structures with self-cleaning and self-sensing abilities.
These advantages could help in the photocatalytic decomposition of pollutants and structural health
monitoring of the concrete structures. The nanomaterials have a great potential for applications in
smart infrastructure based on high-strength concrete structures.

Keywords: carbon nanotubes; cement-based materials; concrete infrastructure; graphene; graphene

oxide; mechanical strength; nanomaterials; nano-Al2 O3 ; nano-Fe2 O3 ; nano-SiO2 ; nano-TiO2 ;
smart infrastructure

1. Introduction
Construction engineering requires materials that enhance the mechanical properties of the
cement-based composites for modern concrete infrastructure. For instance, the compressive, tensile
and flexural strength of concrete structures need to be improved. For this, nanomaterials can be mixed
with cementitious matrices to obtain concrete with high mechanical strength [1–10]. Nanotechnology
can facilitate the development of nanomaterials incorporated into cement-based materials to increase
their mechanical strength [11–25], decreasing their environment impact [26]. The CO2 emissions

Materials 2019, 12, 3548; doi:10.3390/ma12213548 www.mdpi.com/journal/materials

Materials 2019, 12, 3548 2 of 40

generated during the production of ordinary Portland cement can represent approximately between
5% and 7% of the world man-made emissions of this gas [27,28]. A main challenge of the cement
industry is the reduction of the CO2 emissions. One alternative solution is the construction of concrete
structures with higher mechanical strength and higher durability, which will decrease their maintenance
requirements or need for early replacement. Thus, the concrete structures can have thinner sections,
which will require less quantity of cement-based composites for their construction.
The cement-based materials can be mixed with nanomaterials such as nano-silica (nano-SiO2 ),
nano-alumina (nano-Al2 O3 ), nano-ferric oxide (nano-Fe2 O3 ), nano-titanium oxide (nano-TiO2 ), carbon
nanotubes (CNTs), graphene and graphene oxide. In recent years, several researchers [29–49]
have studied the incorporation of nanomaterials into cement-based materials. The mixture of
cementitious composites and nanomaterials can increase the mechanical strength of the resulting
concrete structures. Thus, the life cycle of these structures can be extended or they can require
smaller amounts of steel reinforcing bars. A common nanomaterial employed in cement-based
composites is nano-silica. This material accelerates the cement hydration due to the generation
of calcium-silicate-hydrate (C–S–H) and dissolution of tricalcium silicates (C3 S) [50]. In addition,
this acceleration of cement hydration is caused by the nano-silica acting as a seed for nucleation
of C–S–H [50]. Nano-silica can improve the durability, workability and mechanical properties of
cement-based materials [51–59]. On other hand, nano-Al2 O3 particles can increase the compressive
strength of cement-based materials [41,60–63]. Al2 O3 nanofibers with a dosage of 0.25% by cement
weight may enhance the compressive strength of cement-based materials by up to 30% [50]. Another
nanomaterial that can be added to cementitious matrices is nano-Fe2 O3 . Optimal values of this
nanomaterial improve the compressive strength of concrete specimens [64,65]. The cement added with
TiO2 nanoparticles can be used to build a photocatalytic concrete with self-cleaning and air-purification
characteristics [66]. This concrete type can allow effective photocatalytic decomposition of pollutants,
including volatile organic compounds, carbon monoxide, chlorophenols and aldehydes generated
from automobiles and industrial emissions [66–68]. Also, graphene family nanomaterials can be
incorporated into cement composites to enhance their mechanical strength and durability, as well as
provide self-sensing abilities [69–72]. Other novel properties of cement-based materials containing
nanomaterials are their low electrical resistivity and self-sensing capabilities [73]. For instance,
cement-based composites with CNTs have strain-sensing abilities, which may allow the measurement
of their electrical resistance under applied loads [74]. It represents an advantage to obtain strain-sensing
concrete structure systems for structural health monitoring [75,76].
This review includes recent studies about the effects on the mechanical strength, durability and
workability of cement-based composites due to the incorporation of nanomaterials such as nano-SiO2 ,
nano-Fe2 O3 , nano-TiO2 , nano-Al2 O3 , CNTs, graphene and graphene oxide. In addition, these studies
include nanomaterials that provide self-cleaning and self-sensing abilities to concrete structures. Also,
the main challenges of using nanomaterials in cement-based materials are discussed.

2. Nanomaterials in Cement-Based Materials

2.1. Nano-Silica (Nano-SiO2 )

Nano-silica is a nanomaterial employed for civil engineering applications that can replace
micro-silica and silica fume. Nano-silica reacts with lime during the cement hydration process and it
generates a C–S–H gel that may improve the mechanical strength and durability of concrete. A good
dispersion of nano-silica into cement-based materials can accelerate the hydration process of cement
paste, allowing a denser microstructure. On the other hand, an excessive number of nanoparticles can
cause agglomeration due to their high surface energy, which will provide a non-uniform dispersion.
Figure 1 shows the scale ranges of several materials used in concrete fabrication [77].
Materials 2019, 12, 3548 3 of 40

Figure 1. Scale range of several materials used in the concrete fabrication. Reprinted with permission
from [77]. Copyright©2017, Higher Education Press and Springer-Verlag, Berlin/Heidelberg.

Flores-Vivian et al. [77] used Portland cement containing nano-silica to modify the rheological
performance and improve the durability and strength. They used a nano-silica content of 0.25% by
weight of cement-based materials. Other researchers such as Braz de Abreu et al. [22] reported the use
of stabilized nano-silica particles (between 3 and 200 nm in size) in Brazilian-type CP V ARI PLUS
Portland cement. They fabricated three types of concrete mixes: a reference concrete, a concrete added
with stabilized nano-silica and a concrete including stabilized nano-silica with silica fume. After,
they studied the results of concrete compressive strength tests at curing ages of 3, 7 and 28 days.
The concrete compressive strength with only stabilized nano-silica increased up to 27%, 20% and
11% at 28 days compared with the reference concrete. On the contrary, the concrete with stabilized
nano-silica and silica fume registered even higher compressive strength values (i.e., 28%, 37% and
24% at 28 days) compared to the control concrete. Thus, a mixture of nano-silica and silica fume with
Portland cement generated a concrete with higher compressive strength.
Heidari and Tavakoli [78] fabricated a mixture using nano-silica and ceramic powder.
They investigated the properties of ceramic power based on the ASTM C 618 standard, using
92% as material in the mixture. In this mixture, the cement is replaced with ceramic powder (phase
A). In the second phase (phase B), the ceramic powder percentage is reduced, and the nano-silica
is added. They employed the binder content as a constant (320 kg/m3 ) and a water-cement ratio of
0.5. During phase A, mixtures were made with a ceramic powder percentage of 0%, 10%, 15%, 20%,
25%, 30% and 40% of the cement weight using the same proportion of aggregates and water. During
phase B, mixtures are made with 0.5% and 1% of nanosilica and different ceramic powder content of
10%, 15%, 20% and 25% of the cement weight. All concrete mixtures are fabricated considering the
ASTM C192 standard. The results of the compressive strength tests of the concrete (phase A) were
obtained with different curing ages (7, 28, 56 and 91 days). These results show that the concrete strength
proportionally decreases with the amount of ceramic powder added to the concrete. The concrete
specimen containing 1% of nano-silica and 10% of ceramic powder improved its compressive strength.
The impact on the pozzolanic reaction of nano-SiO2 is more effective at an early age.
Supit and Shaikh [79] determined the durability properties of high-volume fly ash concrete with
addition of nano-silica. They used type I Portland cement and different series of mixtures with a
Materials 2019, 12, 3548 4 of 40

water-cement ratio of 0.40. Compressive strength tests for all concrete mixtures were measured at
ages of 3, 7, 28, 56 and 90 days. The incorporation of nano-silica into ordinary concrete increased
the compressive strength reaching up to 150% more at early ages. For ages of 28, 56 and 90 days,
the compressive strength showed an increment between 45% and 75%. The nano-silica accelerated the
hydration process and allowed a cementitious matrix with denser microstructure. The 4% nano-silica-
modified concrete decreased its water absorption (between two and three times lower) in comparison
to concrete without nano-silica. The resistance of chloride penetration was studied at ages of 28 and
90 days, in which the mixture with 2% nano-silica registered the lowest penetration value. Based on
microstructure analysis, nano-silica-modified concrete mixtures presented denser microstructures.
Thus, nano-silica modified concretes could be classified as low permeability concretes.
In order to reinforce reactive powder concrete (RPC), Han et al. [80] added nano-SiO2 -coated
TiO2 (NSCT) to RPC. These nanomaterials were studied by scanning electron microscopy (SEM),
thermogravimetry (TG) analysis and powder X-ray diffraction (XRD). The acceleration of cement
hydration due to the effect of the nucleus played a dominant role in the first days. The CH crystals
particles size registered a reduction when the content of NSCT was increased (see Figure 2). The flexural
and compressive strength of NSCT reinforced RPC (NSCTRRPC) specimens were investigated at
curing ages of 3 and 28 days, considering different contents of NSCT (i.e., 1%, 3% and 5% by cement
weight). The NSCTRRPC specimens enhanced their flexural and compressive strength in comparison
to RPC specimens without NSCT. Figures 3 and 4 depict the flexural and compressive strength of
NSCTRRPC specimens at curing ages of 3 and 28 days. For 3% NSCT dosage at a curing age of
3 days, a maximum flexural strength value (9.77 MPa) of the NSCTRRPC specimen was achieved.
It represents an increment of 83.3% compared with the RPC without NSCT. For curing age of 28 days
and 5% NSCT content, the flexural strength (14.38 MPa) of the NSCTRRPC specimen was increased
up to 87% with respect to RPC without NSCT. Thus, NSCT increases the flexural strength of RCP
specimens at both early age (3 days) and later age (28 days). The composites with NSCT registered
small increments in their compressive strength at curing age of 3 days. On the contrary, maximum
levels of the compressive strength of NSCT modified composites were measured at a curing age of
28 days. Thus, the highest compressive strength (111.75 MPa) of NSCTRRPC specimens is obtained
with 3% NSCT dosage. This strength value registered an increase of 12.26% in comparison with RPC
without NCST. However, the flexural strength of NSCTRRPC specimens had higher increment levels
than that of compressive strength for the same test composites. This is caused by the NSCT that
significantly enhances the toughness of the RPC [80].
Li et al. [81] examined the properties of ultra-high-performance concrete, which is obtained with
particles of nano-limestone (nano-CaCO3 ) and nano-silica. They used type I Portland cement and
fly ash, and silica fume as binding agents. The percentages of nano-silica and nano-limestone by
cement weight were of 0.5%, 1.0%, 1.5% and 2.0% and 2.0%, 3.0% and 4.0%, respectively. The mixture
workability was reduced with respect the control specimen and it was maintained when the amount
of nano-limestone is increased. This is due to the small size of nanoparticles that are found on the
surface, leaving less water to contribute towards fluidity. The compressive and tensile strength of
concretes including nano-limestone and nano-silica were improved with respect to concretes without
any additions. The microstructure with highest values of density and mechanical strength was
obtained with content levels of 1% nano-silica and 3% nano-limestone, respectively. The mechanical
strength of concrete containing nano-silica and nano-limestone is increased with the reduction of the
water-cement ratio.
Sadeghi et al. [82] reported non-destructive compressive strength tests of self-compacting concretes
added with steel fibers, polypropylene and nano-silica. They employed the ultrasonic pulse velocity
technique in concrete to register mechanical strength of concrete specimens. These concrete specimens
(100 × 100 × 100 mm3 ) were fabricated based on II Portland cement at ages of 7, 28 and 90 days.
In addition, they used 40 different types of mixtures considering 2%, 4% and 6% of replacement with
nano-silica and superplasticizer. In the specimens were measured the wave transmission velocity
Materials 2019, 12, 3548 5 of 40

and compressive strength using the exponential relationship between both parameters. An increment
of steel fiber volume above 3% increased the wave pulse transmission velocity in the specimens.
The compressive strength and wave pulse transmission velocity increased when the percentage of
nano-silica achieved above 4% of cement weight; however, both decreased afterwards.

Figure 2. SEM micrographs of CH crystals in concrete with nano-SiO2 -coated TiO2 at curing age of
28 days (20,000×): (a) sample T0; (b) sample T3; (c) sample T5. Reprinted with permission from [80].
Copyright©2017, Elsevier B.V.

Figure 3. Flexural strength of NSCTRRPC test specimens with different values of NSCT content at
curing age of 3 and 28 days. Reprinted with permission from [80]. Copyright©2017, Elsevier B.V.
Materials 2019, 12, 3548 6 of 40

Figure 4. Compressive strength of NSCTRRPC test specimens with different values of NSCT content at
curing age of 3 and 28 days. Reprinted with permission from [80]. Copyright©2017, Elsevier B.V.

Najigivi et al. [83] implemented tests using ordinary Portland cement and different nano-silica
particles types according to average size. They named each one with the letters N and M, which both
particle types reached an amorphous structure with a high pozzolanic reaction. These researchers
used a water-cement ratio of 0.40, including nano-silica particles with proportions of 0.5%, 1.0%, 1.5%
and 2.0% within the N particles and 2% in the M particles. In all the combinations of these tests,
both nano-silica particles types decreased the concrete fluidity. The lime-cure concrete with maximum
compressive strength was achieved using 2% nano-silica particles of M type with quicklime solution.
This concrete reached the maximum values of compressive strength (40.2 MPa, 53.5 MPa and 57.1 MPa)
at curing ages of 7, 28 and 90 days. This increment is due to the calcium hydroxide compounds reacted
with nano-silica at a superficial level, generating additional C–S–H gel.
Zhang et al. [84] investigated the durability of concrete specimens containing nano-silica and steel
fiber. They used five different contents of nano-silica (1%, 3%, 5%, 7% and 9%) and five-volume levels
of steel fiber (0.5%, 1%, 1.5%, 2% and 2.5%). The durability tests of concrete specimens included the
carbonation and cracking resistance, and permeability and freezing-thawing resistance. The durability
tests are examined considering the carbonation depth of the specimens, total cracking area per unit area
of the concrete specimen, cracks number, relative dynamic elastic modulus of the samples obtained
after of the freezing-thawing cycles, and permeation depth of the water. For instance, a reduction in
both the generated cracks number and water permeation depth of the concrete specimens can improve
the concrete durability. Figures 5 and 6 show the total cracking area per unit area and cracks number of
concrete samples containing 15% fly ash and five different nano-silica dosages. The cracks number in
the concrete specimens decreased when the nano-silica dosages increased from 1% to 7%. The minimum
number of cracks is achieved with 7% nano-silica dosage, but this number is increased when the
nano-silica content is 9%. In addition, the total cracking area significantly decreased for nano-silica
contents between 3% and 5%. Although, a nano-silica dosage of 9% caused an increment of 71.8%
of the total cracking area compared with 5% nano-silica content. On the contrary, water permeation
depth of the concrete specimens is showed in Figure 7. When the nano-silica content increments
between 1% and 5%, the water permeation depth of the concrete specimens is significantly reduced.
This improvement level decreases for nano-silica dosages of 7% and 9%, respectively. Based on these
results, the nano-silica added concrete specimens enhanced their durability when the nano-silica
content is within a certain limit. However, a high content of nano-silica could affect the durability of
the concrete.
Materials 2019, 12, 3548 7 of 40

Figure 5. Influence of nano-silica dosage on the total cracking area per area unit of concrete specimens.
Reprinted with permission from [84]. Copyright©2019, MDPI AG.

Figure 6. Effect of nano-silica dosage on the cracks number of concrete samples. Reprinted with
permission from [84]. Copyright©2019, MDPI AG.

Figure 7. Effect of nano-silica dosage on the water permeation depth of concrete samples. Reprinted
with permission from [84]. Copyright©2019, MDPI AG.

Tavakoli et al. [85] reported the effect on the compressive strength caused by addition of silica
fume and nano-silica in concrete samples at curing age of 7, 28 and 56 days. They used type II Portland
cement with different percentages of nano-silica (0.5% and 1%) and silica fume (5% and 10%) by
cement weight. For each case, concrete samples containing nano-silica and silica fume increased their
compressive strength compared to control specimen without these materials. The concrete samples
achieved the highest compressive strength (52.9 MPa) using 10% of silica fume and 1% of nano-silica
particles at curing age of 56 days. This strength value is 42.2% higher than that of the concrete sample
without nano-silica and silica fume. More investigations about of nano-silica modified cement were
Materials 2019, 12, 3548 8 of 40

reported by Nazerigivi and Najigivi [86]. They studied the influence on the mechanical strength of
concrete specimens caused by incorporation of two different nano-silica sizes (15 nm and 80 nm) with
percentages of 0.5%, 1.0%, 1.5% and 2.0% by cement weight. They employed ordinary Portland cement
and 16 different concrete samples and one control concrete sample for each mechanical test type,
as indicated Table 1. A water-to-binder ratio of 0.40 was used into all the concrete samples. With lime
solution, these samples are cured at ages of 7, 28 and 90 days. Tables 1–3 indicate the measurements of
the compressive, split tensile and flexural strength of all the concrete samples. For the three curing ages,
the nano-silica added concrete samples improved their compressive strength with respect to that of the
control specimen. The compressive strength had a gradual increment when the nano-silica dosage was
increased up to 2% of 15 nm plus 1.5% of 80 nm; after, it had a small decrease. The generation of C–S–H
gel may be accelerated due to ultra-high specific surface and ultra-fine particle size of nano-silica
incorporated in concrete samples [82]. The split tensile and flexural strength of all the nano-silica
modified concrete specimens were improved with respect to the control sample. Both split tensile and
flexural strength registered gradual increments with the incorporation of nano-silica up to 2% of 15 nm
plus 1.5% of 80 nm; after, these mechanical strengths had a small reduction. It could be caused because
the total quantity of nano-silica is higher than that to obtain the lime-silica hydration reaction [82].
Mastali and Dalvand [87] reported a theoretical and experimental study of the effects on the
mechanical properties of concrete samples due to the presence of 1.0% nano-silica and 7% silica fume,
respectively. They realized 270 tests with different designs of self-compacting concrete, in which the
impact resistance and mechanical properties of concrete samples were enhanced. The incorporation of
nano-silica and silica fume in the cement of silica fume and self-compacting concrete increased 70% its
impact resistance for the first crack. Fiber reinforced specimens with water-cement ratio of 0.34 and
0.27 registered the highest average of tensile and flexural strength, respectively.

Table 1. Compressive strength of concrete specimens containing several nano-silica contents. Reprinted
with permission from [86]. Copyright©2019, Elsevier B.V.

Improvement of Compressive
Nano-Silica Compressive Strength (MPa)
Strength (%)
Sample
15 nm 80 nm
7 Days 28 Days 90 Days 7 Days 28 Days 90 Days
Nanoparticle Nanoparticle
C0
0 0 26.3 34.8 40.3 0 0 0
(control)
N1 0.5 0.5 28.2 38.4 44.9 7.2 10.3 11.4
N2 0.5 1 30.3 41.3 49.2 15.2 18.7 22.1
N3 0.5 1.5 32.9 44.2 53.0 25.1 27.0 31.5
N4 0.5 2 35.2 46.8 57.6 33.8 34.5 42.9
N5 1 0.5 31 42.5 50.7 17.9 22.1 25.8
N6 1 1 33.4 46.2 54.1 27.0 32.8 34.2
N7 1 1.5 36.3 47.5 58.2 38.0 36.5 44.4
N8 1 2 40.7 50 63.3 54.8 43.7 57.1
N9 1.5 0.5 35.2 47 56.1 33.8 35.1 39.2
N10 1.5 1 37.2 49.1 59.8 41.4 41.1 48.4
N11 1.5 1.5 41.3 52.2 64.7 57.0 50.0 60.5
N12 1.5 2 46.4 58.7 69.3 76.4 68.7 72.0
N13 2 0.5 39 50.3 63.4 48.3 44.5 57.3
N14 2 1 41.9 54 67.2 59.3 55.2 66.7
N15 2 1.5 52.1 63.7 78.1 98.1 83.0 93.8
N16 2 2 50.3 61 75.2 91.3 75.3 86.6
Materials 2019, 12, 3548 9 of 40

Table 2. Split tensile strength of concrete specimens containing several nano-silica contents. Reprinted
with permission from [86]. Copyright©2019, Elsevier B.V.

Improvement of Split Tensile

Nano-Silica Split Tensile Strength (MPa)
Strength (%)
Sample
15 nm 80 nm
7 Days 28 Days 90 Days 7 Days 28 Days 90 Days
Nanoparticle Nanoparticle
C0
0 0 1.3 1.5 1.9 0 0 0
(control)
N1 0.5 0.5 1.8 2 2.7 38.5 33.3 42.1
N2 0.5 1 2.1 2.4 3 61.5 60.0 57.9
N3 0.5 1.5 2.5 2.9 3.5 92.3 93.3 84.2
N4 0.5 2 3 3.3 3.9 130.8 120.0 105.3
N5 1 0.5 2.2 2.8 3.2 69.2 86.7 68.4
N6 1 1 2.7 3.1 3.8 107.7 106.7 100.0
N7 1 1.5 3.1 3.7 4.2 138.5 146.7 121.1
N8 1 2 3.8 4.2 4.8 192.3 180.0 152.6
N9 1.5 0.5 2.9 3.3 4.1 123.1 120.0 115.8
N10 1.5 1 3.3 3.8 4.6 153.8 153.3 142.1
N11 1.5 1.5 4.1 4.5 5.2 215.4 200.0 173.7
N12 1.5 2 4.4 4.8 5.7 238.5 220.0 200.0
N13 2 0.5 3.6 4 4.9 176.9 166.7 157.9
N14 2 1 4.5 4.8 5.5 246.2 220.0 189.5
N15 2 1.5 4.9 4.3 5.9 276.9 186.7 210.5
N16 2 2 4.3 4.8 5.1 230.8 220.0 168.4

Table 3. Flexural strength of concrete specimens containing several nano-silica contents. Reprinted
with permission from [86]. Copyright©2019, Elsevier B.V.

Improvement of Flexural
Nano-Silica Flexural Strength (MPa)
Strength (%)
Sample
15 nm 80 nm
7 Days 28 Days 90 Days 7 Days 28 Days 90 Days
Nanoparticle Nanoparticle
C0
0 0 4 4.2 4.5 0 0 0
(control)
N1 0.5 0.5 4.4 4.5 5 10.0 7.1 11.1
N2 0.5 1 4.6 4.9 5.3 15.0 16.7 17.8
N3 0.5 1.5 5.1 5.2 5.7 27.5 23.8 26.7
N4 0.5 2 5.4 5.6 6 35.0 33.3 33.3
N5 1 0.5 4.6 5.1 5.4 15.0 21.4 20.0
N6 1 1 5.3 5.5 5.9 32.5 31.0 31.1
N7 1 1.5 5.5 5.8 6.3 37.5 38.1 40.0
N8 1 2 5.9 6.2 6.7 47.5 47.6 48.9
N9 1.5 0.5 5.4 5.7 6.1 35.0 35.7 35.6
N10 1.5 1 5.6 6 6.6 40.0 42.9 46.7
N11 1.5 1.5 6.2 6.5 7 55.0 54.8 55.6
N12 1.5 2 6.5 6.8 7.3 62.5 61.9 62.2
N13 2 0.5 5.8 6.2 6.8 45.0 47.6 51.1
N14 2 1 6.5 6.7 7.2 62.5 59.5 60.0
N15 2 1.5 7 7.3 7.8 75.0 73.8 73.3
N16 2 2 6.8 7 7.2 70.0 66.7 60.0

Mohammed et al. [88] evaluated the influence on the properties of concrete due to the nano-silica
inclusion. This nano-silica incorporation caused a reduction of 13% in the pore amount of the
cementitious paste. They studied the relationships that improved the compression strength of the
concrete. The workability was modified negatively, which was not affected with the incorporation
of superplasticizer to the concrete paste. When the nano-silica inclusion was increased in the
experimentation, the permeability and infiltration rate were reduced based on the SEM results.
The incorporation of nano-silica optimal dosage in concrete samples may improve their
compressive, tensile and flexural strength. The nano-silica added in cement with other materials such
Materials 2019, 12, 3548 10 of 40

as polypropylene, glass and steel fibers with fixed proportions can increase the mechanical properties
of the concrete. Concretes with nano-silica absorbed Ca(OH)2 crystals, filling the voids of the C–S–H
structure, leading to a denser microstructure.

2.2. Nano-Ferric Oxide (Nano-Fe2 O3 )

The optimal addition of nano-Fe2 O3 in concrete specimens may improve their compressive
strength. In addition, the volume electrical resistance of cement mortars with inclusion of nano-Fe2 O3
can be altered through the applied load, allowing the measure of compressive stress [73]. It can be
used for structural heath monitoring of concrete structures without require additional sensors.
Fang et al. [89] measured the mechanical properties of cement samples with different additions of
nano-Fe2 O3 (3%, 5% and 10% by cement weight) at ages of 7, 14 and 28 days. Figure 8 shows the SEM
image of cement specimens with different additions of nano-Fe2 O3 . When the nano-Fe2 O3 content
increases then the surface morphology is denser. For all the measurements, the addition of nano-Fe2 O3
in cement mortars increased their compressive strength compared to control mortar. Maximum values
of the compressive strength of the cement samples were achieved using 10% of nano-Fe2 O3 content.
For this nano-Fe2 O3 dosage at curing ages of 7, 14 and 28 days, the compressive strength of the cement
mortar was increased up to 66.81%, 69.76% and 25.20%, respectively.

Figure 8. SEM image of concrete specimens with addition of nano-Fe2 O3 (a) 0%; (b) 3%; (c) 5%; (d) 10%.
Reprinted with permission from [89]. Copyright©2018, Atlantis Press.

Rashad [90] presented a review the effects of nano-Fe2 O3 , nano-Al2 O3 , nano-Fe3 O4 and nanoclay on
some properties of cement composites. These properties were the mechanical strength, hydration heat,
water absorption, workability, setting time and durability. For instance, the inclusion of nano-Fe2 O3 in
the cementitious matrix decreased the water absorption and heat rate values as well as accelerated the
peak times. Moreover, the workability of the composite was reduced when the nano-Fe2 O3 content
Materials 2019, 12, 3548 11 of 40

was increased. On the other hand, nano-Fe2 O3 (0.5%–5% in concretes and 0.5%–10% in mortars) added
into the cementitious matrix improved the compressive strength. Nazari et al. [91] also studied the
workability of concrete including nano-Fe2 O3 . For this case, cement was partially substituted with
nano-Fe2 O3 (i.e., 0%, 0.5%, 1%, 1.5% and 2% by cement weight) and a water to binder ratio of 0.4
was employed. The workability of concrete is decreased when the nano-Fe2 O3 dosage is increased.
In addition, Nazari and Riahi [92] developed two models using genetic programming and artificial
neural networks to predict the percentage of water absorption and split tensile strength of concrete
samples containing nano-Fe2 O3 .
Khoshakhlagh et al. [93] studied the changes of the concrete properties achieved by adding
different percentages (1%–5% by cement weight) of nano-Fe2 O3 and superplasticizer. The flexural,
compressive and tensile strength, and the water permeability of the concrete specimens were improved
with the incorporation of nano-Fe2 O3 up to 4% by cement weight. The content of nano-Fe2 O3 up
to 4wt.% of the concrete specimens increased the coefficient of water absorption. The concrete
specimens with nano-Fe2 O3 enhanced their hydration heat, workability and the compressive, flexural
and tensile strength.

2.3. Nano-Titanium Oxide (Nano-TiO2 )

The addition of nano-TiO2 in concrete specimens can provide self-cleaning properties to the
concrete. The concrete containing these nanoparticles can allow a photocatalytic degradation of
pollutants (e.g., VOCs, CO, NOx , aldehydes and chlorophenols) from industrial and automobile
emissions. However, this effect is less efficient with aging due to carbonatation [94,95].

Figure 9. Cont.
Materials 2019, 12, 3548 12 of 40

Figure 9. Examples of photocatalytic cement-based coatings that contain TiO2 thin film: (a) parking lot
view (Phoenix, AZ, USA) and (b) bike lane (Brooklyn, NY, USA). Reprinted with permission from [23].
Copyright©2016, Higher Education Press and Springer-Verlag Berlin/Heidelberg.

Figure 9 depicts two applications of photocatalytic cement-based coatings, which allows a

self-cleaning effect in function the decomposition of gases and organic pollutions [23]. This is due
to a TiO2 thin film on the concrete surface that can provide active oxygen under UV light present
in sunlight. Thus, it catalyzes the degradation of organic matters located at the nano-TiO2 coated
concrete surface [27]. The concrete surface is cleaned with the rainwater, which can prevent the
buildup of dirt. Another important characteristic of nano-TiO2 is the chemical stability and low
price in comparison with other materials. Moreover, nano-TiO2 can enhance the resistance to water
permeability of cement-based structures [25]. Figure 10 depicts the SEM image of fracture surfaces
of cementitious composites considering two sizes of nano-TiO2 [96]. Wang et al. [97] investigated
the mechanical and physical properties of cement mortar specimens considering different contents of
nano-TiO2 under curing temperatures of 0, 5, 10 and 20 ◦ C. They used natural river sand, Portland
cement (type I ordinary), and TiO2 nanoparticles with size of 15 nm. In the experimental tests were
used nano-TiO2 dosages of 1%, 2%, 3%, 4% and 5% by cement weight, respectively. In the fabrication
of the specimens, the nano-TiO2 was dispersed in water through ultrasonication. After, cement and
sand are mixed during 1 minute. Then, the well-dispersed nano-TiO2 was added and mixed during
60 seconds and after water was incorporated. In the following stage, the mortars are collocated into
molds and cured using different temperatures. For the specimens were used a water to binder ratio of
0.5. Figure 11 depicts the SEM images of cement pastes including 2 wt.% nano-TiO2 , at curing age
of 28 days under different temperatures. The compressive strength characterization is determined
according to ASTM C109 [98] employing a hydraulic testing machine under a controlled load of
1350 N/s. The flexural strength test was evaluated regarding the ASTM C293 [99]. This characterization
is determined at curing ages of 3, 7, 28 and 56 days. Figure 11 depicts the results of the hydration
degree of the mortar specimens. First, hydration degree of the mortar specimens enhanced through the
increment of the nano-TiO2 dosage. TiO2 nanoparticles can supply an extra space for the precipitation
of hydration products. Figures 12 and 13 depict the response of the compressive and flexural strength
of the cement mortar samples. Both compressive and flexural strength registered downward trend
at low curing temperature. On contrary, flexural and compressive strength of mortar specimens
containing nano-TiO2 had fast increment with respect to ordinary mortar until that the nano-TiO2
content achieved up to 2 wt.%. This increase slowed down for TiO2 nanoparticles dosages higher than
2 wt.%. The enhanced strength of mortar samples is caused by TiO2 nanoparticles that facilitated the
cement hydration and filled the pores in C–S–H gels [97]. These nanoparticles present large surface
area to volume ratio, allowing an extra surface area to precipitate hydration products. In addition,
TiO2 nanoparticles form a bond between them self and C–S–H gel that improves their strength [97].
Materials 2019, 12, 3548 13 of 40

Figure 10. SEM image of the fracture surfaces considering: (a) control cementitious composites (1200×);
(b) nano-TiO2 (50 nm size) modified cementitious composites (1200×); (c) nano-TiO2 (500 nm size)
modified cementitious composites (1200×); (d) aggregations of nano-TiO2 (50 nm size) in cementitious
composites (1200×). Reprinted with permission from [96]. Copyright©2019, Elsevier B.V.

Feng et al. [100] examined the microstructures of concrete matrices incorporating nano-TiO2 as
well as the mechanical properties of the cement pastes. Figure 14 is a SEM image of TiO2 nanoparticles
and their selected area electron diffraction. The incorporation of nano-TiO2 (0.1%, 0.5%, 1.0% and 1.5%
by cement weight) in cement paste using a water-cement ratio of 0.4 improved the flexural strength
(4.52%, 8.00%, 8.26% and 6.71%) at 28 days age.
Jalal et al. [101] studied the characteristics of high resistance self-compacting concrete containing
fly ash and nano-TiO2 . They used Portland cement that was replaced up to 15% weight of waste ash
and up to 5% weight of nano-TiO2 . The addition of nano-TiO2 in the concrete improved the consistency
and reduced the segregation probability. Considering the water absorption and capillarity, a significant
decrease was obtained due to the nano-TiO2 .
Materials 2019, 12, 3548 14 of 40

Figure 11. SEM images of cement samples with addition of 2 wt.% nano-TiO2 cured under temperatures
of (a) 0 ◦ C, (b) 5 ◦ C, (c) 10 ◦ C, and (d) 20 ◦ C at 28 days. Reprinted with permission from [97].
Copyright©2018, Hindawi.

The weight losses in concrete samples were caused by the rapid formation of hydrated products.
The self-compacting concrete with nano-TiO2 registered a microstructure more refined, which enhanced
the resistance to mechanic failures. Other researchers, Yu et al. [102] reported the improvement of
concrete microstructure incorporating nano-TiO2 , which increased its mechanical strength. The TiO2
nanoparticles catalyze the decomposition of harmful gases in the air. In addition, the concrete with
nano-TiO2 achieved a maximum compressive strength that was 7% higher in comparison with the
non-added nanoparticle concrete. In addition, Yu et al. [102] investigated the changes of temperatures
that can induce cracks and accelerate the hydration reaction.
Chunping et al. [103] investigated the durability of ultra-high performance concrete due to
the incorporation of nano-TiO2 . This concrete added with 1% nano-TiO2 improved its mechanical
properties. They investigated the effects on the dry shrinkage, carbonation resistance, freeze-thaw
resistance and resistance to chloride ingress. The addition of nano-TiO2 in concrete could allow it
a self-cleaning and photocatalytic behavior. In addition, the normal concrete containing nano-TiO2
could decrease the capillary porosity.
Materials 2019, 12, 3548 15 of 40

Figure 12. Compressive strength of cement mortar samples incorporating different nano-TiO2 dosages.
Reprinted with permission from [97]. Copyright©2018, Hindawi.

Figure 13. Flexural strength of cement mortar samples containing different nano-TiO2 dosages.
Reprinted with permission from [97]. Copyright©2018, Hindawi.
Materials 2019, 12, 3548 16 of 40

Figure 14. TEM image of the morphology of the TiO2 nanoparticles and their selected area electron
diffraction (SAED). Reprinted with permission from [100]. Copyright©2013, American Chemical Society.

2.4. Nano-Alumina (Al2 O3 )

The use of nano-Al2 O3 can accelerate the formation process of C–S–H gel, especially at early-ages,
which enhances the strength of composites [104]. For instance, Muzenski et al. [50] fabricated
ultra-high strength cement-based materials using Al2 O3 nanofibers with a content of 0.25% by weight
of cementitious materials, which improved the compressive strength up to 200 MPa. This represents an
increment of 30% in comparison to material strength with only 1% of silica fume. This high compressive
strength was achieved with low amount of silica fume. This improved performance is caused by the
nanofibers that act as a seed to generate hydration products and contribute the reinforcement for the
C–S–H formations, which decrease the number of micro-cracks. In addition, to reach the maximum
mechanical performance of the cement-based materials is necessary a suitable dispersion of the Al2 O3
nanofibers. A longer dispersion time could reduce the fibers agglomeration, allowing the enhance
of mechanical performance. For instance, the compressive strength at 28 days age achieved higher
values for specimens with Al2 O3 nanofibers dispersed for 3 h. Nevertheless, higher quantities of
Al2 O3 nanofibers and supplementary cementitious materials did not increase the mechanical behavior
of the cement-based materials. Figure 15a,b depicts SEM images of the Al2 O3 nanofibers diluted in
cement pastes.

Figure 15. SEM image of the Al2 O3 nanofibers diluted in cement pastes at (a) 9000× magnification and
(b) 20,000× magnification. Reprinted with permission from [50]. Copyright© 2019, Elsevier B.V.
Materials 2019, 12, 3548 17 of 40

Yang et al. [105] investigated the effect of nano-Al2 O3 on the chloride-binding capacity of cement
paste samples. These samples were prepared with nano-Al2 O3 dosages of 0.5%, 1.0%, 3.0% and
5%. The chloride-binding capacity was examined using conventional equilibrium tests, in which the
samples were exposed with a NaCl solution at 0.05 mol/L, 0.1 mol/L, 0.3 mol/L, 0.5 mol/L and 1.0 mol/L,
respectively. Based on the experimental results, the bound chloride content had an increase of 37.2% at
NaCl solution (0.05 mol/L) by adding 5.0% of nano-Al2 O3 . Thus, an appropriate adding of nano-Al2 O3
improved the chloride-binding of cement paste samples.
Mohseni at al. [106] studied the effects of nano-alumina and rice husk ash (RHA) in polypropylene
fiber (PPF)-reinforced cement mortars. The RHA is an agricultural waste material, which can be recycled
to obtain economic and environmental benefits. Figure 16 shows the SEM images of nano-alumina
and RHA. The compressive strength of the mortar samples is increased up to 18% and 20% due to
the addition of 3% nano-Al2 O3 with 20% RHA at 28 and 90 days. The flexural strength of the mortar
samples increased up to 34% and 41% by adding 3% nano-Al2 O3 with 10% RHA. This addition of
nano-Al2 O3 generated a denser microstructure in the mortar samples.

Figure 16. SEM image of the (a) nano-Al2 O3 and (b) rice husk ash. Reprinted with permission
from [106]. Copyright© 2016, Elsevier B.V.

Barbhuiya et al. [107] examined the influence of the incorporation of nano-Al2 O3 on the
microstructural properties of the cement paste hydrated at 7 days age. Ordinary Portland cement is
substituted with nano-Al2 O3 powder with 2% and 4% by cement weight and the water-cement ratio is
fixed to 0.4. In this early-age, they did not note changes at the compressive strength of the cement
specimen at early age.
Based on the XRD analysis, Barbhuiya et al. [107] did not find a new crystalline phase developed
by adding nano-Al2 O3 within 7 days of curing. They reported the generation of dense microstructure
with larger crystal of portlandite within the cement matrix due to the nano-Al2 O3 addition, as shown in
Figures 17 and 18. Gowda et al. [108] reported the influence of nano-Al2 O3 in the water absorption and
electrical resistivity of cement mortars. They used 1%, 3% and 5% of nano-Al2 O3 by cement weight.
The water absorption had a small reduction with the addition of 1% and 3% nano-Al2 O3 . However,
the water absorption registered a small increment with the addition of 5% nano-Al2 O3 . The highest
electrical resistivity of the cement mortar is achieved with 5% nano-Al2 O3 .
Materials 2019, 12, 3548 18 of 40

Figure 17. SEM image of 2% nano-Al2 O3 by weight of cement paste hydrated up to 7 days. Reprinted
with permission from [107]. Copyright© 2014, Elsevier Ltd.

Figure 18. SEM image of 4% nano-Al2 O3 by weight of cement paste hydrated up to 7 days. Reprinted
with permission from [107]. Copyright© 2014, Elsevier B.V.

2.5. Carbon Nanotubes (CNTs)

Recently, several researchers [109–123] have reported the effects of CNTs on the electrical and
mechanical properties of concrete samples. For instance, CNTs can decrease the formation and growth
of micro-cracks in concrete. The CNTs have important mechanical and electrical properties, including
their high strength and high conductivity. For instance, CNTs have high mechanical performance
with high aspect ratios (length to diameter ratio) that may generate stronger cement composites [27].
The CNTs cement-based composites have strain-sensing behavior that can measure their electrical
parameters under applied loads [124]. This behavior can allow the development of strain-sensing
systems of concrete structures for potential applications of damage detection and structural health
monitoring [75,125].
García-Macías et al. [124] developed a micromechanics model to determine the piezoresistive
behavior of cement-based nanocomposites incorporating CNTs and considering the waviness and
non-uniform distributions of nanoinclusions. In order to validate the theoretical model, they tested
cement-based samples that were doped with multi-walled CNTs (MWCNTS) and exposed to uniaxial
compression. These samples were fabricated of concrete, mortar and composite cement paste. Figure 19
depicts the SEM pictures of the MWCNTs dispersion in water solution after sonication and in a cement
mortar sample. For the compression loads on the MWCNTs reinforced cement-based composites,
they used an equipment of servo-controlled pneumatic universal testing with load capacity of 14 kN,
as shown in Figure 20a,b. For the cement paste, mortar and concrete samples are incorporated
Materials 2019, 12, 3548 19 of 40

MWCNTs with electrical conductivity between 101 and 104 S/m. Figure 21a–c illustrates the response
of the electrical conductivity of different cement-based composites using the theoretical model and
experimental setup. The cement paste, mortar and concrete specimens used filler concentrations of
1%, 0.75% and 0.75% by cement weight. The proposed analytical model may predict the electrical
resistance performance of MWCNTs reinforced cement-based materials under compression loads.
Ruan et al. [118] reported the influence of different types and dosages of MWCNTs on the mechanical
properties of RPC under water or heat curing. They fabricated RPC including four types of MWCNTs
with dosages of 0%, 0.25% and 0.50% with water/heat curing, respectively. The mechanical performance
of the MWCNTs filled RFC specimens were examined. This mechanical performance considered
the flexural strength, fracture energy, compressive/ toughness and flexural strength to compressive
strength ratio. The fabrication of the RPC specimens included MWCNTs, water, water reducer, fly ash,
quartz sand, cement and silica fume. The cement, silica fume and quartz sand ratio was 1:0.25:1.1.
In addition, 20% of cement was substituted by fly ash to enhance the mobility of the mixtures and
decrease the cement amount. The four types of MWCNTs used were classified as T1 (functionalized
MWCNTs with carboxyl groups), T2 (functionalized MWCNTs with hydroxyl groups), T3 (helical
MWCNTs through catalytic cracking) and T4 (nickel-coated MWCNTs).

Figure 19. SEM images of the MWCNTs dispersion in (a) water suspensions after sonication and (b) in
a mortar specimen after curing. Reprinted with permission from [124]. Copyright© 2017, Elsevier B.V.

Figure 20. (a) Compression load versus time and (b) uniaxial testing machine used in the MWCNTs
reinforced cement-based specimens. Reprinted with permission from [124]. Copyright© 2017,
Elsevier B.V.
Materials 2019, 12, 3548 20 of 40

Figure 21. Results of the theoretical and experimental electrical resistance versus applied mechanical
strain for (a) cement paste, (b) mortar and (c) concrete samples. Reprinted with permission from [124].
Copyright© 2017, Elsevier B.V.

Figure 22 illustrates the flexural strengths of the MWCNTs filled RPC under water curing.
With exception of the specimen filled with 0.5% MWCNTs dosage of T3, all the others specimens filled
with dosages of 0.25% and 0.50% MWCNTs showed enhanced flexural strength. The specimen T2
with 0.25% MWCNTs content had the maximum increase (27.2%) of the flexural strength. However,
the specimen with 0.50% MWCNTs content registered a decrease (3.8%) of the flexural strength. For the
specimens T1, T2 and T3, the flexural strength had better results for low dosage of MWCNTs than
that by high dosage of MWCNTs. In addition, the incorporation of the four types of MWCNTs with
dosages of 0.25% and 0.50% improved the compressive strength of the RPC specimens under water
curing. The compressive strength increased 18.1% with the incorporation of 0.50% MWCNTs content,
compared with the RPC without MWCNTs. The dosage of MWCNTs improved the compressive
toughness of all the RPC specimens with water curing, as shown Figure 23. The highest compressive
toughness was measured in the specimen T2 with 0.25% MWCNTs content, which represented an
increase of 39.2% in comparison to the RPC without MWCNTs. Figure 24a,b depicts SEM images of the
wide distribution network of MWCNTs in RPC, which can improve the mechanical properties of RPC.

Figure 22. Flexural strengths of the MWCNTs reinforced RPC specimens under water curing. Reprinted
with permission from [118]. Copyright© 2018, Elsevier B.V.
Materials 2019, 12, 3548 21 of 40

Figure 23. Compressive strengths of the MWCNTs reinforced RPC specimens under water curing.
Reprinted with permission from [118]. Copyright© 2018, Elsevier B.V.

Figure 24. (a,b) SEM images of the extensive distribution of MWCNTs in RPC. Reprinted with
permission from [118]. Copyright© 2018, Elsevier B.V.

Lushnikova and Zaoui [120] studied the effect of different types of CNTs incorporated into
cement specimens. They used molecular dynamics simulations to determine the influence of CNTs
on the mechanical properties of C–S–H such as shear modulus, bulk modulus, elastic constants
and Poisson ratio. The results of these simulations registered an improvement of all the studied
mechanical properties. Thus, the CNTs are nanomaterials that could enhance the mechanical properties
of concrete. Moreover, Sedaghatdoost and Behfarnia [121] examined the influence on the mechanical
properties of the Portland cement caused by addition of MWCNTs at the ratios between 0 and 0.15%
by weight of cement specimens. These specimens were heated using high temperatures (200–800 ◦ C).
The incorporation of 0.1% MWCNT by cement weight improved the compressive, tensile and flexural
strength by 35%, 8%, and 11.2%, respectively. In addition, the cement paste was more stable and denser
due to the addition of MWCNT. Also, Hawreen and Bogas [122] studied the effects on the long-term
creep and shrinkage of concrete due to the incorporation of different types of CNTs. They used
concretes with 0.05%–0.5% of unfunctionalized and functionalized CNTs and water to cement ratios of
0.35–0.55. The compressive strength of the concrete with CNTs was increased up to 21%. The addition
of CNTs caused a reduction in the early and long-term shrinkage of concrete up to 54% and 15%,
Materials 2019, 12, 3548 22 of 40

respectively. The concrete with addition of CNTs had 17%–18% lower long-term creep in comparison
to the concrete without CNTs. Carbon nanotubes are innovative materials for the construction industry
that can decrease the formation of nano-cracks. Moreover, the inclusion of CNTs in concrete may
increase the compressive and flexural strength of the concrete.

2.6. Graphene-Based Nanomaterials

Recent studies [126–147] have examined the performance of cement-based materials incorporating
graphene family nanomaterials (GFN) such as graphene, graphene oxide (GO), reduced graphene
oxide (rGO), and graphene nanosheets (GNS). These nanomaterials have extraordinary electrical,
mechanical, chemical and thermal properties. Thus, GFN reinforced cement-based materials can
improve their structural strength and durability, as well as allow self-cleaning surfaces and self-sensing
abilities [148–158].
Hu et al. [158] fabricated cement composite including nano-silica coated GO, which enhanced its
mechanical properties. The compressive strengths of cement composites containing GO and nano-silica
coated GO were studied at curing ages of 1, 3, 7 and 28 days. The nano-silica coated GO reinforced
cement composites increased their compressive strength up to 120.6%, 124.1%, 126.7% and 133%
compared to plain cement with curing ages of 1, 3, 7 and 28 days, respectively. For the GO reinforced
cement composites without nano-silica, their compressive strengths improved up to 106.0%, 106.7%,
112.2% and 113.6% with respect to plain cement at curing time of 1 day, 3 days, 7 days and 28 days.
The coated nano-silica on GO allowed a finer surface structure and better dispersion, which helped
to eliminate the agglomeration of GO in pore solution. The nano-silica coated GO promoted the
deposition and growth of C–S–H, refining the cement composite microstructure and improving their
macro-mechanical properties. Moreover, Hu et al. [159] functionalized GO via triethanolamine (TEA),
which was added into oil well cement (OWC) to enhance its mechanical behavior. The incorporation
of TEA-GO and GO was at 0.3 wt.%, keeping a fixed water-to-cement ratio of 0.44. First, they
mixed GO/TEA-GO power with water and after added cement within 15 s. In the second stage, the
cement was collocated in the cup of Waring blender at 4000 rpm and after was mixing during 15 s
at 120,000 rpm. Finally, the cement composites are cured at 60 ◦ C for 1, 3, 7 and 28 days. Both GO
and TEA-GO had good dispersion in water; although, TEA-GO with smaller size reported better
uniformity. The TEA-GO incorporated to cement allows nucleation sites and acts as seeds to provide
the cement hydration. In order to evalue the influence of GO/TEA-GO on the mechanical properties of
cement composite, compressive and flexural strength were obtained through mechanical hydraulic
pressure testing machine. For the compressive strength tests, the TEA-GO reinforced samples (50.8
× 50.8 × 50.8 mm3 ) were characterized a loading rate of 1.2 KN/s. On the other hand, the flexural
strength tests used TEA-GO reinforced samples (160 × 40 × 40 mm3 ) under a loading rate of 0.2 KN/s.
Figure 25 illustrates the average compressive and flexural strengths of GO and TEA-GO reinforced
cement samples. The TEA-GO reinforced cement samples presented higher increments (9.4%–31%) of
the compressive strength than that of GO reinforced cement (4.1%–17.2% ). This is due to that TEA-GO
modified cement provides crystals more mature and fewer pores and cracks compared to blank cement
and GO reinforced cement samples (see Figure 26). Therefore, the TEA-GO significantly refines the
microstructure of cement specimens. On the contrary, the TEA-GO reinforced cement samples achieved
the higher increments (8.1%–36.7%) with respect to those of cement incorporating GO (7.8%–20%).
The TEA-GO enhanced the mechanical performance of cement due to the increment of hydration
degree and limitation to crack propagation. Figure 27 depicts SEM images of the cracks types in three
different OWC composites. In the blank cement sample, the cracks penetrate in a straight-through form.
For GO reinforced cement sample, the cracks are thinner with random branches. Finally, the cement
containing TEA-GO registers fewer cracks with thinner dimensions.
Materials 2019, 12, 3548 23 of 40

Figure 25. Response of the (a) compressive and (b) flexural strength of OWC composites containing
GO and TEA-GO. Reprinted with permission from [159]. Copyright© 2019, Elsevier B.V.

Figure 26. SEM image of the (a) blank OWC sample, (b) GO reinforced OWC specimen and (c) TEA-GO
reinforced OWC specimen after compressive strength test at age 28 days. Reprinted with permission
from [159]. Copyright© 2019, Elsevier B.V.

Figure 27. SEM images of the (a) plain OWC matrix including a straight-through crack, (b) GO/OWC
specimen containing fine cracks and (c) TEA-GO/OWC specimen. Reprinted with permission from [159].
Copyright© 2019, Elsevier B.V.

Tao et al. [160] investigated the influence of graphene nanoplatelets (GNPs) on the microstructure,
pore structure, piezoresistive and mechanical behavior of cement mortar. They quantitatively examined
the piezoresistive performance of GNP-reinforced cement mortars exposed to cyclic compressive loads.
A PI 42.5 cement is used as binder and natural quartz sands are employed as aggregates. Different
dosages (M0 = 0%, M1 = 0.05%, M2 = 0.1%, M3 = 0.5% and M4 = 1%) of GNPs by cement weight
were incorporated in cement matrix. The compressive and flexural strength of the GNP-reinforced
cement mortars were characterized through a 25 KN high-performance fatigue testing machine. For the
compressive and flexural tests were employed loading rates of 144 kN/min and 3 kN/min, respectively.
The four-probe method is employed to measure the piezoresistive properties of the cement mortars
including GNPs. The cement mortars are dried at 80 ◦ C during 24 h to eliminate the capillary water,
which affects the piezoresistive response [161]. Figure 28 illustrates the fracture surfaces of cement
Materials 2019, 12, 3548 24 of 40

mortars containing different GNPs dosages. Later, the cement mortars specimens, regarding the
probes and cables, are examined using the mechanical testing machine (see Figure 29). First, the initial
resistance of the specimens is determined at stable voltage. Then, the external loads are applied to
specimens using constant loading rate of 0.5 kN/s and the piezoresistive properties are obtained through
an Instron actuator. Figure 30 depicts the compressive and flexural strengths of the cement mortars.
Both strengths firstly increment their values and after decrease when the GNP dosage increases.

Figure 28. SEM images of the cement mortars added with different GNP content: (a) M0 (0%), (b) M1
(0.05%), (c) M2 (0.1%), (d) M3 (0.5) and (e) M4 (1%). Reprinted with permission from [160]. Copyright©
2019, Elsevier B.V.

Figure 29. Measurement setup of piezoresistive test of the GNP-added cement mortars under cyclic
compressions. Reprinted with permission from [160]. Copyright© 2019, Elsevier B.V.
Materials 2019, 12, 3548 25 of 40

Figure 30. Experimental results of the (a) compressive and (b) flexural strengths of the GNP reinforced
cement mortars. Reprinted with permission from [160]. Copyright© 2019, Elsevier B.V.

Higher magnitudes of compressive and flexural strengths (53.6 MPa and 8.9 MPa, respectively)
are reached in the cement mortar with GNP dosage of 0.25% (M1) by cement weight. These values
represent increments of 8.3% and 15.6% compared with the compressive and flexural strengths of the
cement mortar without GNP. However, the values of both strengths decrease when the GNP dosages
exceed 0.05%. Thus, cement hydrates with homogeneous spatial distribution could be obtained with
appropriate values of GNPs dispersed in cement matrix.
Qureshi and Panesar [162] characterized the influence of GO and rGO on the performance of
cement-based composite. They investigated the microstructural properties of GO and rGO using X-ray
diffraction (XRD), optical microscope, Fourier-transform infrared spectroscopy (FTIR), SEM, Energy
dispersive X-ray (EDS) and Raman spectroscopy techniques. The average C:O ratio of 54.46 and 82.18 in
GO and rGO, respectively, were employed in the cement-based materials. To enhance the dispersibility
of rGO in water, rGO was processed with superplasticizer. The dosages of both GO and rGO were of
0.02%, 0.04% and 0.06% of cement weight. To reach uniform mixture and efficient dispersion of both
GO and rGO in the cement specimens, a water to cement ratio of 0.45 is implemented. In comparison
with the control cement sample without GO and rGO, the final setting time and workability of GO
reinforced cement specimens gradually decreased using higher GO content up to 0.06% of cement
weight. This is caused by the dominant oxygen functional groups and hydrophilic behavior of GO.
On the other hand, final setting time and workability of rGO-added cement specimens increased
with respect to the control cement sample. It is due to the superplasticizer content and the almost
hydrophobic behavior of rGO. The GO composites had greater dosage of C–S–H and Ca(OH)2 than
the rGO composites at ages of 1, 7 and 28 days. In addition, the GO composites showed micropores
filled with crystalline compounds and C–S–H gel. For the rGO composites was found random pore
filling nature with ettringite elements. Figure 31 depicts the SEM-EDX results of the microstructure
of GO composite pores. Based on the EDX and SEM results of GO and rGO, these nanomaterials
present suitable compatibility with cement hydration products, reinforcing the microstructure of the
cement composites. Figure 32 depicts the response of the flexural strength and compressive of cement
specimens added with GO and rGO at curing age of 28 days. In comparison to control cement sample,
cement composites incorporated with 0.02%, 0.04% and 0.06% GO and rGO dosages had an increase of
10.2%, 7.8% and 10.6 %, and 9.6%, 13.3% and 14.9%, respectively. This is due to the high number of
functional groups of GO in chemical bonding with cement hydration products and the high mechanical
strength of rGO.
Materials 2019, 12, 3548 26 of 40

Figure 31. SEM-EDX results of the microstructure of GO composite pores in: (a) 0.06% GO composite,
(b) amplification of (a) showing a surface growth nature of ettringite and flakes structures, (c) a small
pore of 0.02% GO and (d) a small pore of 0.04% GO. Reprinted with permission from [162]. Copyright©
2019, Elsevier B.V.

Figure 32. Experimental response of the (a) compressive and (b) flexural strength of GO and rGO
reinforced cement specimens at curing age of 28 days. Reprinted with permission from [162].
Copyright© 2019, Elsevier B.V.

Krystet et al. [163] studied the mechanical properties and microstructure of cementitious materials
with addition of electrochemically exfoliated graphene (EEG). EEG enhanced the mechanical properties,
microstructure and workability of cementitious materials. EEG did not provide aggregate in alkaline
environment and the cement mortars incorporating EEG did not decrease its workability and fluidity.
The mixture of 0.05 wt.% of graphene with ordinary Portland cement improved the compressive
and tensile strength of the cement material up to 79% and 8%, respectively. EEG contributes to
Materials 2019, 12, 3548 27 of 40

hydration reactions of calcium silicates, allowing an intense generation of C–S–H phase and a
compact microstructure.
Kaur and Kothiyal [164] compared the effect of polycarboxylate superplasticizer (PCE-SP) added
GO and functionalized CNT (SP@GO and SP@FCNT) on the mechanical properties of cement
nanocomposites (CNCs). They used two types of SPs to alter the GO and FCNTs structural features, and
to enhance the dispersion of these nanomaterials in aqueous solution and cement matrix. The stabilized
GO and FCNT allowed to enhance the mechanical strength of the CNC specimens. After, they fabricated
three cubes of CNC specimens (70.6 mm × 70.6 mm × 70.6 mm3 ) containing SP@GO and SP@FCNT
with different dosages (i.e., 0.02%, 0.04%, 0.08% and 0.16% by cement weight). These specimens were
water curing at ages of 7, 14 and 28 days to characterize their mechanical strength. The mechanical
tests were done using universal testing machine, applying load at the rate of 3.8 kN/s and 0.5 kN/s,
respectively. Figures 33 and 34 show the measurements of average compressive and flexural strength of
the SP@GO and SP@FCNT modified CNC specimens. With respect to cement specimen, the maximum
values of compressive and tensile strengths of CNC specimens were improved up to 23.2% and 38.5%
due to addition of 0.02% and 0.08% SP@GO by cement weight, respectively. On the other hand,
addition of 0.08% and 0.04% of SP@FCNT by cement weight enhanced the compressive and tensile
strengths of the CNC specimens by 16.5% and 35.8%, respectively. Figure 35 depicts FE-SEM images of
CNC specimens containing different SP@GO dosages.

Figure 33. Experimental results of the (a) compressive and (b) flexural strength of SP@GO modified
CNC specimens at curing ages of 7, 14 and 28 days. Reprinted with permission from [164]. Copyright©
2019, Elsevier B.V.
Materials 2019, 12, 3548 28 of 40

Figure 34. Experimental results of the (a) compressive and (b) flexural strength of SP@FCNT modified
CNC specimens at curing ages of 7, 14 and 28 days. Reprinted with permission from [164]. Copyright©
2019, Elsevier B.V.

Figure 35. FE-SEM images of CNC specimens incorporating (a) 0.02% SP@GO, (b) 0.04% SP@GO,
(c) 0.08% SP@GO and (d) 0.16% SP@GO at curing age of 28 days. Reprinted with permission from [164].
Copyright© 2019, Elsevier B.V.

The addition of graphene family nanomaterials in cement composites can enhance their mechanical
strength. This will allow the construction of lighter concrete components with extended durability,
thus, the consumption of concrete components could be decreased. This will help with the reduction
of the gas pollutants resulting from concrete production.

3. Challenges
The nanotechnology has allowed the fabrication of nanomaterials that can be incorporated in
cement-based materials to generate higher mechanical properties of the concrete structures. The effect
of the nanomaterials on the performance of cement-based materials includes the enhance of their
compressive, tensile and flexural strength, reduction of the total porosity (i.e., refinement of the
microstructure), acceleration of C–S–H gel generation and increment of Young modulus. Furthermore,
Materials 2019, 12, 3548 29 of 40

incorporation of nanomaterials such as nano-TiO2 and CNTs can provide self-cleaning and self-sensing
properties, respectively, of the products obtained with cement-based materials. To achieve the optimal
mechanical properties of the cement-based materials it is very important to mix a suitable dosage of
nanomaterial with the cement-based materials. For instance, excessive quantities of nanomaterials
added to cement can result in lower compressive, tensile and flexural strength of the cement-based
structures. This is caused by nonhomogeneous dispersion of nanomaterials in the cement paste.
Thus, the mechanical properties of the nanomaterial reinforced cement-based materials depend of
several factors such as the dosage and type of nanomaterial, dispersion method, curing days and
curing method. Between these factors, the dispersion method can have a significantly effect on the
performance of the nanomaterial reinforced concrete.
An important challenge for the application of nanomaterials in the construction industry is the
development of efficient methods for the dispersion of nanomaterials in cement samples. An alternative
solution to incorporate the nanomaterial into cement-based materials consists in the dispersion of
the nanomaterial in water before of incorporating it to the dry components of the cement-based
materials [165]. For this case, ultrasonic dispersion can be employed as an effective method for the
dispersion of the nanomaterials, although, this method requires electrical energy that increases its cost.
A bad dispersion of the nanomaterials into cement specimens and the formation of great amount of
agglomerates may alter the kinetics of the hydration process, modifying the properties of the cement
specimens. For instance, Singh et al. [166] reported that the method used to incorporate nano-silica
into cement composites can affect the porosity and mechanical properties of the composites. A bad
nano-silica dispersion in cement-based materials may generate voids and weak zones, altering the
mechanical properties of the materials. Surfactants such plasticizers and superplasticizers can be used
to improve the dispersion of nanomaterials in cement-based materials [51,167,168]. Thus, surface
active agents can enhance the homogeneity of dispersion due to the generation of aggregates around
nanoparticles [169]. This good dispersion is achieved because of both hydrophobic and hydrophilic
groups. The nanomaterials interact with the hydrophobic groups and the hydrophilic groups decrease
the water-surface tension, increasing the dispersion of the nanomaterials [167]. Nevertheless, several
surfactants (e.g., polymeric matrices) employed for the dispersion of nanoparticles can affect the
cement hydration kinetics. Figure 36 depicts a nanomaterial dispersion process employed to obtain a
cement-based composite.

Figure 36. Schematic view of a common nanomaterial dispersion process employed to fabricate a
cement-based composite. Reprinted with permission from [167]. Copyright©2018, MDPI AG.

To develop the large scale production of these modified cement-based materials it will be necessary
to develop an efficient nanomaterial dispersion method that allows a stable and satisfactory dispersion
in cement-based materials [167]. However, the re-agglomeration of the nanoparticles may change their
size, which could affect their behavior of nanomaterials in cement-based materials [170].
The application nanomaterials in cement-based composites is attractive due to that enhances their
mechanical properties only using small dosages of nanomaterials. However, the high cost of these
nanomaterials is a limitation to achieve their commercial application in cementitious materials. In the
case of graphene and graphene oxide, their fabrication scale is small and relatively expensive. In the
Materials 2019, 12, 3548 30 of 40

future, an important challenge is the reduction of fabrication costs of the nanomaterials. For instance,
SiO2 nanoparticles may be generated with low cost from hydrothermal solutions generated due the
magmatic ore intrusion [77]. Thus, nano-silica and other minerals can be recovered when the steam is
condensed in water during the operation of a geothermal power plant [77].
Moreover, another challenge is the optimal dosage determination of the nanomaterial added
in the cement paste to obtain the higher mechanical strength and greater durability. To meet this
goal, more studies about the effect of different types of nanomaterials on the mechanical properties
of cement-based materials are required. These studies must include the effect of the combination of
nanomaterials with other cementitious materials. Thus, the optimal quantities of the combination of
these materials must be examined to find the best mechanical behavior of the cement-based materials.
The main challenge of the use of carbon nanotubes (CNTs)/nanofibers in cement paste is the dispersion
due to their strong self-attraction and high hydrophobicity [171,172]. This poor dispersion may
cause defects zones in cement/CNTs composites, which constrain the use of CNTs in cementitious
matrices [27]. Thus, more investigations must be made with respect to developing methods to improve
the dispersion of CNTs in cement-based composites. For example, some researchers [173,174] have
studied chemical and surface modification methods for carbon nanotubes to improve their dispersion
and bonding between carbon nanotubes and the matrix. Other studies [175–177] had examined the
mechanical properties of cement samples, which were prepared with different combinations of carbon
nanotubes and nano-silica. In addition, future researches must consider prediction models of the
relationship between external mechanical deformations and electrical resistivity of cement-based
composites incorporating CNTs.
In addition, the future applications of nanomaterials in the construction industry will require one
to consider the local environmental conditions (e.g., elements of the local environmental dust). These
conditions could damage the performance of the concrete, reducing its durability and increasing the
cost of maintenance. For instance, The Jubilee Church in Rome (2003) was one of the first buildings
that used self-cleaning and reinforced concrete [178–180]. This construction had three iconic shells
constructed from 2001 and 2002, which employed precast panels with photocatalytic nano-TiO2
particles. Thus, the nano-TiO2 particles could absorb energy from light and employ it to achieve
a photocatalytic degradation of pollutions. In 2019, Cardellicchio [179,180] reported a study about
premature evidence of decay of the three shells that showed failure of their self-cleaning performance.
This study considered the material pathologies and their possible damage sources. The surfaces of the
shells still contain nano-TiO2 particles in the form of anatine, which was detected by this study through
chemical analysis. Nonetheless, the self-cleaning properties of the shells with nano-TiO2 are only
activated when both the sunlight allows the redox of pollutant and the photo-induced hydrophilicity
permits the cleaning of the shells [180]. For this case, the hydrophilic characteristic is limited by two
main conditions. One condition is linked with common composition of the pozzolanic powder in
Rome that cannot be oxidized by titanium dioxide. Another condition is the abrasive effect of the
rainwater on the surface of the shells that improves the superficial roughness, increases the bond
between powder particles and concrete [180]. The erosive action occurs on the convex surface, which
was registered by a colorimetric analysis showing a tendency towards whitish-grey hue caused by the
scattering of the sunlight. These two conditions generate a patina which decreases the photocatalytic
effect of the surface of the concrete shells (see Figure 37). The efficiency of the nano-TiO2 particles
incorporated in concrete is affected by the porosity and roughness of the concrete surface. The porosity
of the concrete surface may allow the water retention and its roughness may help the adhesion of
powder on the surface. The chemical and abrasive characteristics of pozzolanic powder may decrease
the efficiency of the self-cleaning of the nano-TiO2 added concrete. Therefore, future buildings that use
concrete with self-cleaning properties may be affected by powder of volcanic origins or precipitations
incorporating desert dust [180].
Materials 2019, 12, 3548 31 of 40

Figure 37. View of the damages on the surface of the self-cleaning concrete shells of Jubilee Church
in Rome, which were caused by the local environmental dust. Reprinted with permission from [180].
Copyright©2019, Taylor & Francis Group.

More investigations about new nanomaterials to improve the mechanical properties of

cement-based composites are required. In addition, to achieve the commercial application of these
nanomaterials reinforced cement-based composites is necessary to know the effect of the nanomaterials
on the mechanical properties of these composites. Therefore, future researches must include the
development of novel theoretical models that can predict the mechanical properties of the cement-based
materials as function of dosage level of the nanomaterials. Also, more researches about the impact of the
nanomaterials in the public health and environment must be developed. There are few studies about
the effects of the nanomaterials used in cement-based materials on the public health and environment.
For instance, Lee et al. [181] reported some effects of nanoparticles used in the construction industry
on environment health and safety. Lam et al. [182] presented a review about the carbon nanotube
toxicity, which could produce pulmonary inflammation and cardiac toxicity. Moreover, nano-TiO2
could generate inflammation in mammalian cells [183]. Thus, many researches must be done to reduce
the negative impacts of the nanomaterials on the health and environment. In addition, more studies
about the bioavailability and environment mobility of nanomaterials required to be done [182].

4. Conclusions
The incorporation of nanomaterials in concrete can improve their compressive, tensile and
flexural strength. Recent investigations had considered nanomaterials such as nano-silica, nano-titania,
nano-ferric oxide, nano-alumina, CNT, graphene and GO. The addition of these nanomaterials in
concrete can achieved denser microstructures, decreasing the water absorption. The workability of
the concrete could be improved by adding these nanomaterials. The nano-TiO2 modified concrete
can provide it self-cleaning properties and other benefits to help the environment clean. In addition,
nano-TiO2 added in concrete can allow the photocatalytic degradation of pollutants (e.g.; NOx , VOCs,
CO, chlorophenols, and aldehydes) from automobile and industrial emissions. The CNTs reinforced
cement-based composites can have self-sensing abilities for applications of structural health monitoring
or damage detection. In addition, graphene and GO added in cement-based materials can increase their
mechanical strength and durability, as well as develop self-cleaning surfaces and self-sensing abilities.
In the construction industry, the fabrication of cement-based composites can generate high levels
of CO2 gas. To address this problem, one solution is the addition of nanomaterials to cement-based
Materials 2019, 12, 3548 32 of 40

composites, which can provide structural components with high mechanical strength and great
durability. Thus, the maintenance requirements and replacement frequency of the cement-based
structural components can be decreased. These advantages can allow the reduction of the percentage
of cement used in the construction industry. This in turn will decrease the CO2 emissions caused by
the cement fabrication process.
The application of nanotechnology in cement-based materials is still in a research stage. The results
of experimental tests of nanomaterials-reinforced cement specimens have demonstrated that they can
enhance the mechanical strength and durability of the resultng concretes. Moreover, these nanomaterials
can allow a novel generation of smart cement-based composites with strain-sensing abilities for damage
inspection and structural health monitoring.

Author Contributions: K.P.B.-G. and A.H.-M. contributed with the sub-sections of nano-silica, nano-Fe2 O3
and nano-Al2 O3 ; J.M.S.-L. supervised all the sections of the manuscript; S.A.Z.-C. reviewed the sections
of introduction and challenges, and A.L.H.-M. wrote the sections of nano-TiO2 , carbon nanotubes and
graphene-based nanomaterials.
Funding: This research was supported by the project “PFCE 2019 DES Técnica Veracruz 30MSU0940B-21”.
Conflicts of Interest: The authors declare no conflict of interest.

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