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Influence of nanoparticles on fluidity and

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ARTICLE in CONSTRUCTION AND BUILDING MATERIALS DECEMBER 2015
Impact Factor: 2.3 DOI: 10.1016/j.conbuildmat.2015.10.149

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Construction and Building Materials 101 (2015) 892901

Contents lists available at ScienceDirect

Construction and Building Materials

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

Influence of nanoparticles on fluidity and mechanical properties of

cement mortar
Jintao Liu, Qinghua Li , Shilang Xu
Institute of Advanced Engineering Structures and Materials, Zhejiang University, Hangzhou 310058, China

h i g h l i g h t s

Nanoparticles content affected directly on the fluidity of cement mortar.

Mechanical properties of cement mortars modified nanoparticles were tested.

Increasing nano-ZnO content significantly restrains the hydration of mortar.

Enhancement mechanism of nano-SiO2 on mortar was studied by SEM and XRD.

a r t i c l e

i n f o

Article history:
Received 1 May 2015
Received in revised form 16 October 2015
Accepted 22 October 2015

Keywords:
Nanoparticles
Cement mortar
Mechanical properties
Microstructure

a b s t r a c t
Nanoparticles are potentially effective microstructural reinforcements for cementitious composites.
Many properties of composites may change with the addition of nanoparticles. In this work, the workability, mechanical and microstructure properties of mortar containing four kinds of nanoparticles were
evaluated, and these four kinds of nanoparticles were nano-Al2O3, nano-SiO2, nano-TiO2 and nano-ZnO
respectively. Test results showed that the increasing addition of nano-SiO2 and nano-Al2O3 led to the
increased water demand while nano-TiO2 and nano-ZnO had little effect on the mortar fluidity. With
3% (by weight of cement) nano-SiO2 particles, the 7 days flexural and compressive strength increased
by 17.8% and 9.5% respectively. Nano-ZnO prolonged the setting time of mortar significantly, furthermore, the compressive strength was much lower than that of control specimen at early age. The influence
of nanoparticles on the hydration degree, fluidity and mechanical properties of cementitious mixes were
analyzed by using Scanning Electron Microscope (SEM) and X-ray Diffraction (XRD).
2015 Elsevier Ltd. All rights reserved.

1. Introduction
The highly active mineral admixtures, such as slag, fly ash, silica
fume and clay, have been wildly used to reduce cement
consumption and improve the performance of concrete due to
the environmental and sustainable issues. Most particle sizes of
these pozzolanic materials are in micron-size, while about 70% of
cement hydration products of calcium silicate hydrate gel particles
are in nano-size. Some nano materials have shown promise in
enhancing the mechanical performance of concrete, and the composition of nanoparticles presents a new way to improve
microstructures of concrete at the nanoscale [1,2]. Nanoparticles
can be seen as macromolecules clusters, and they exhibit special
mechanical, optical and electrical properties because of their
nanometer effects [35]. They have been well applied in biological,
energy and medical field, however, the application of nanoparticles
Corresponding author.
E-mail address: liqinghua@zju.edu.cn (Q. Li).
http://dx.doi.org/10.1016/j.conbuildmat.2015.10.149
0950-0618/ 2015 Elsevier Ltd. All rights reserved.

in the building engineering area was not very popular. Theoretically, the nanostructure materials may also have broad prospect
and important value in cement-based materials.
In recent years, studies of nanoparticle composites have been
concentrated on nanoparticles/cement paste, nanoparticles/mortar
and nanoparticles/concrete composites. It was reported that the
pozzolanic activity of nano-SiO2 was much higher than that of silica
fume [6,7]. The compressive strengths of mortars with different
amounts of nano-SiO2 were all higher than those of mortars containing silica fume at 7 and 28 days. In some other studies, nanoSiO2 and nano-Al2O3 were found to decrease crystalline Ca(OH)2
amount and accelerate CSH (calcium silicate hydrate) gel formation, especially at early ages, which promote the development composites strength [8,9]. In addition, they also improved the resistance
to water permeability and bonding strength of ITZ (interface transition zone) of composites [1012]. However, conflicting and divergent conclusions have been obtained regarding the reinforcement
of these nanoparticles on cementitious composites. Luo et al. comparatively studied the effect of two types of nano-Al2O3 on the

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J. Liu et al. / Construction and Building Materials 101 (2015) 892901

hydration of cement paste. The amounts of CSH gel and CAH

(calcium aluminate hydrate) salts produced in specimens with
nano-Al2O3 (c phase) additive were relatively higher than those
with nano-Al2O3 (a phase) additive, moreover, nano-Al2O3 with
smaller diameter was easy to cluster together in water [13]. In
another study, no changes were noticed in the early-age compressive strength with nano-Al2O3 addition, but SEM revealed the
formation of much denser microstructure with larger crystals of
portlandite [14]. Furthermore, the elastic modulus of mortar
increased by 143% when the content of nano-Al2O3 was 5 wt%,
but the compressive strength of mortar was lower than control at
28 days [15]. Previous studies indicated that the nanoparticle size,
type and mixture proportion all have certain effects on the performance of composites. On one hand, smaller size and higher content
of nanoparticles can efficiently improve the hydration of cement;
but on the other hand, nanoparticles aggregate easily because of
Van der Waals force and electrostatic action, which significantly
reduces the fluidity and strength of the matrix.
Nano-TiO2 has wide applications in exhaust gas and wastewater
treatment, and it has been proven to be very effective for selfcleaning and de-pollution of concrete [16]. Similar to nano-SiO2,
nano-TiO2 also could decrease crystalline Ca(OH)2 amount and
accelerate CSH gel formation, especially at early ages [17]. The
abrasion resistances of concretes containing nano-TiO2 and nanoSiO2 were all significantly improved, while nano-TiO2 had better
performance compared with same amount of nano-SiO2 [9]. Lee
et al. [18]. reported that compressive strength increased with
higher TiO2 nanoparticle replacement at lower water-to-solids
ratio (w/s = 0.40) and strength was not compromised by up to
10% (by weight of cement) TiO2 replacement at higher water-tosolids ratio (w/s = 0.60). Similarly, zinc oxide is another very useful
functional cement additive. Studies have already found that zinc
oxide can strongly delay the setting time and decrease the compressive strength of the samples at short curing ages, moreover,
this effect weakens with aging [19,20]. Activity of nano-ZnO is
higher than that of common zinc oxide, so it can be used as high
performance cement retarder with extremely small amount. However, only a limited number of investigations were dealing with the
effect of nano-TiO2 on mortar. If nano-TiO2 and nano-ZnO nanoparticles are used to produce multifunction concrete, the performance
of the composites is required to be studied.
Therefore, the effects of nanoparticles on the microstructures
and working performances of cement composites, especially the
fluidity and strength, were needed to be complemented and confirmed with further studies. In this research, nano-Al2O3, nanoSiO2, nano-TiO2 and nano-ZnO particles were experimentally
investigated, and the effects of nanoparticles on the early age properties and workability of mortar were examined. In addition, by
using SEM and XRD analyses, the discussions on hydration reaction
mechanism, microstructure, and modality and hydration interface
features of nano composites will provide insight for further
development of nanoparticles reinforced cementitious materials.
2. Experimental procedure
2.1. Materials
Ordinary Portland cement (P O 42.5) was used in this study. Its chemical composition is listed in Table 1. The properties of nanoparticles are shown in Table 2. SEM
diagrams of nanoparticles are shown in Fig. 1. Quartz sand with particle smaller than
2 mm and specific gravity of 2.71 g/cm3 was used as fine aggregate. A poly carboxylic
acid water reducing agent was used to improve the fluidity of cement mortar.
Table 1
Properties of Portland cement (wt%).
Material

Fe2O3

Al2O3

CaO

MgO

SiO2

SO3

Loss

Cement

2.91

4.58

61.08

3.19

19.5

2.5

3.6

2.2. Preparation of the specimens

There is a large Van der Waals force and electrostatic force between the
nanoparticles. If the nanoparticles are added into mortar directly, these nanoparticles aggregations may emerge later as matrix defects in the cement mortar. In order
to obtain a homogeneous mortar, Hobart mixer was used in this experiment. The
mixture proportions are provided in Table 3. First, nanoparticles, cement particles
and sand were placed in the mixing pot and stirred for 2 min. Then, Water
and water reducing agent were poured into mixing pot slowly, and stirred for
6 min. When this mixing process was finished, the mortar appeared to be
homogeneous. Finally, the resulting mortar was then poured into oiled molds
(40 mm  40 mm  160 mm) and vibrated to make good compaction. Specimens
were removed from the mold after 24 h and cured in water at temperature of
20 C. Before the testing, specimens were dried for 24 h at room temperature.
2.3. Testing procedures
The flow measurements allowed us to investigate the workability of these
nano-composites, and NLD-3 jump table was used to test mortar fluidity according
to the national standards of P.R.C GB/T2419-2005. Fresh mortar was filled with
truncated conical model, then, removed the mold and started the machine for
25 s. The table vibration frequency was one time per second, and the diameter of
mortar expansion was measured when the vibration was completed.
The flexural and compressive strength tests of cement mortar were conducted
according to GB/T 17671-1999. Compressive strength was tested at the loading rate
of 0.5 MPa/s at the age of 3, 7 and 28 days by using NYL-60 material testing
machine. Flexural strength was determined by the 3-point bending test (at 50 N/s
loading speed) at 3 and 7 days, and the distance between the two supports was
100 mm. After the tests, some fragments were picked up by forceps and stored in
ethanol to prevent hydration. Then the samples were put in an oven for 24 h before
scanning. In addition, FEI Quanta 650 and XRD were adopted to study the
microstructure and chemical constituents of composites.

3. Experimental results
3.1. Mortar fluidity
The flow table value results of the fresh mortar mixes are shown
in Fig. 2. With different amount of nanoparticles, the mortar
showed different working performance. According to the results,
it should be emphasized that workability of NS and NT series, with
high content of nanoparticles, was much worse than control. The
fluidity (i.e. extended diameter on the electric jump table) of the
control cement mortar sample P (i.e. cement mortar without
nanoparticles) was 280 mm (Fig. 3(a)). Adding nano-SiO2 and
nano-Al2O3 nanoparticles decreased the mortar fluidity significantly, for instance, the mortar fluidity drop to 141 mm when
the mixing amount of nano-SiO2 was up to 3.0 wt%, decreased by
50% compared with control sample. As shown in Fig. 3(b), NS-5
sample has no flow ability after vibration. Similarly, the addition
of nano-Al2O3 reduced the mortar fluidity to 240 mm when the
mixing amount was only 0.25 wt%, and the mortar fluidity
decreased by 45% compared with the control as mixing amount
raised from 0.5 to 1.0 wt% (Fig. 3(c)). The prepared composites possessed of high water adsorption capacity which was derived from
the large specific surface area of nanoparticles. Therefore, to reach
a better workability of nano-SiO2 and nano-Al2O3 mixtures, water
reducing agent content should be increased.
Compared with nano-SiO2 and nano-Al2O3, nano-TiO2 and
nano-ZnO have little effect on the mortar fluidity due to their lower
specific surface area. As shown in Fig. 2, the fluidity of NT series
was increased by adding nano-TiO2 up to 1.0 wt%, then, it was
Table 2
Properties of the nanoparticles.
Species

Color

Diameter
(nm)

Crystal
type

Suface volume
ratio (m2/g)

Purity
(%)

pH
value

SiO2
TiO2
Al2O3
ZnO

White
White
White
White

30 5
25 5
15 5
50 10

Rutile

220 3
5080
180250
50 10

99.5
99.0
99.9
96.0

5.7
6.8
6.8
5.7

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J. Liu et al. / Construction and Building Materials 101 (2015) 892901

Fig. 1. SEM micrograph of (a) nano-SiO2, (b) nano-TiO2, (c) nano-Al2O3 and (d) nano-ZnO particles.

Table 3
Mix proportion design.
Series

No.

Cementitious materials (g)

100

NS

NS-1
NS-2
NS-3
NS-4
NS-5

100
100
100
100
100

NT

NT-1
NT-2
NT-3
NT-4

100
100
100
100

NA

NA-1
NA-2
NA-3
NA-4

100
100
100
100

NZ

NZ-1
NZ-2
NZ-3
NZ-4

100
100
100
100

Cement

NS

NT

NA

Coarse sand (g)

Fine sand (g)

Water (g)

SP (g)

78

32

29

78
78
78
78
78

32
32
32
32
32

29
29
29
29
29

1
1
1
1
1

78
78
78
78

32
32
32
32

29
29
29
29

1
1
1
1

78
78
78
78

32
32
32
32

29
29
29
29

1
1
1
1

78
78
78
78

32
32
32
32

29
29
29
29

1
1
1
1

NZ

0.5
1.0
1.5
2.0
3.0
0.5
1.0
2.0
3.0
0.25
0.5
0.75
1.0
0.5
1.0
1.5
2.0

Notation: NA = nano-Al2O3, NS = nano-SiO2, NT = nano-TiO2, NZ = nano-ZnO.

decreased slightly. Mortar fluidity didnt decline remarkably until

the mixing content of nano-ZnO reached 1.5 wt%, in addition, the

mortar fluidity was decreased to 215 mm when 2.0 wt% nanoparticles was added.

J. Liu et al. / Construction and Building Materials 101 (2015) 892901

895

3.2. Mechanical properties

Fig. 2. Fluidity results of the mortar with different nanoparticles.

Table 4 shows the flexural and compressive strengths of specimens at 3, 7 and 28 days. The results indicate that the compressive
and flexural strengths all increase by adding nano-SiO2. When the
proportion of nano-SiO2 up to 2.0 wt%, the compressive strength
was increased by 13.2%, 9.5% and 7.5% at 3, 7, 28 days, and the flexural strength was increased by 10.1%, 17.8% at 3 and 7 days,
respectively. However, with the growth of age, the compressive
strength rising amplitude reduced slightly. Although nano-SiO2
improved the particle packing density of the mortar and reduced
the number of large volume pores in the matrix, high adding
amount of nano-SiO2 resulted in a sharp decrease of fluidity. As
shown in Fig. 4, several holes were presented on the fractured surface (cross section: 40 mm  40 mm) with nano-SiO2 content rising. The high content of nano-SiO2 led to the growth of pore size,
and the diameter of holes went up to 4.0 mm when the mixing
amount of nano-SiO2 reached 3.0 wt%. Theoretically, nanoparticles
agglomeration would be expected to occur due to the large Van der
Waals forces when the particle concentration reached a certain
value, so the optimal mixing amount of nano-SiO2 was 2.0 wt%
which had little effect on the fluidity.
The addition of nano-TiO2 had little effect on the mechanical
properties of cement mortar. With different mixing amount of
nano-TiO2, the compressive and flexural strengths of specimens
at 3 and 7 days were lower than that of control mortar, but the
compressive strength was similar with P at 28 days. With the
incorporation of 1.0 wt% of nano-Al2O3, the compressive strength
was decreased by 11.9%, 23.4% and 10.8% at 3, 7 and 28 days,
respectively. However, flexural strength of mortar containing
0.5 wt% nano-Al2O3 was found to increase slightly at 3 days. The
specific area of nano-Al2O3 particles is 250 m2/g which is much larger than that of SiO2, so the reaction speed of nano-Al2O3 with calcium hydroxide should be fast. Nano-Al2O3 can react with calcium
hydroxide at early age as follows:

Al2 O3 CaOH2 3H2 O CaAlOH4 2

As stated, nano-Al2O3 can accelerate the reaction but does not

contribute to strength. This can be attributed to the increasing
internal defects of hydration products caused by nano-Al2O3
particles agglomeration.
Nano-ZnO particles can prolong the mortar setting time and
have negative influence on mortar strength. Even adding a minimum dosage of nano-ZnO particles, the mortar curing time was
more than 2 days, and the samples did not meet the demand of test
requirement. With the growth of nano-ZnO particles addition, the
compressive strength declined constantly. As the mixing amount
raised from 0.5 wt% to 2.0 wt%, the compressive strength of NZ series corresponding sample P decreased from 98.4% to 20%. This situation relates to the early hydration reaction between cement and
nano-ZnO which produces a lot of water-insoluble hydratesCa(Zn
(OH)3)22H2O,that will cover on the unhydrated cement particles
and affect further cement hydration. Although Zn ions can promote
the reactions of C3A and generate ettringite (AFt) ultimately which
will help the continually grown of cement hydration products, this
reaction process takes a long time.
3.3. Microstructure

Fig. 3. The fresh mixture of group (a) P, (b) NS-5 and (c) NA-4.

Fig. 5 shows the microstructure of the control group at 3, 7 and

28 days, where the main constituents of the cement mortar are Ca
(OH)2, CSH gel, pores, cracks and unhydrated cement particles,
and AFt sheet also can be seen in the hydration product. Comparing
Fig. 5(b) and (c), the hydration degree of cement mortar was higher
and the matrix became much denser at 28 days. However, there

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J. Liu et al. / Construction and Building Materials 101 (2015) 892901

Table 4
The strength of mortar.
3 days

7 days

28 days

Specimens

Flexural strength
(MPa)

Compressive strength
(MPa)

Flexural strength
(MPa)

7.9

48.6

9.0

Increase %

61.2

NS-1
NS-2
NS-3
NS-4
NS-5

7.5
8.2
8.0
8.7
8.6

5.1
3.8
1.3
10.1
8.9

50.0
53.1
54.1
55.0
53.3

2.9
9.3
11.3
13.2
9.7

9.3
10.1
9.2
10.6
10.7

3.3
12.2
2.2
17.8
18.9

61.6
63.8
65.6
67.0
67.5

0.7
4.2
7.2
9.5
10.3

75.6
78.2
79.4
80.6
78.1

0.8
4.3
5.9
7.5
4.1

NT-1
NT-2
NT-3
NT-4

7.7
7.3
7.4
6.0

2.5
7.6
6.3
24.1

48.8
45.2
45.0
47.2

0.4
7.0
7.4
2.9

8.9
8.9
9.0
9.0

1.1
1.1
0.0
0.0

61.3
56.3
57.5
56.3

0.2
8.0
6.0
8.0

75.6
75.5
74.4
75.0

0.8
0.7
0.8
0.0

NA-1
NA-2
NA-3
NA-4

7.6
8.3
7.6
7.7

3.8
5.1
3.8
2.5

47.1
48.4
45.7
42.8

3.1
0.4
6.0
11.9

8.6
8.8
8.5
8.7

4.4
2.2
5.6
3.3

60.0
57.0
52.8
46.9

2.0
6.9
13.7
23.4

75.0
68.1
67.5
66.9

0.0
9.2
10.0
10.8

73.8
55.6
23.1
15.0

1.6
25.9
69.2
80.0

Increase %

Increase %

NZ-1
NZ-2
NZ-3
NZ-4

Compressive strength
(MPa)
Increase %

Compressive strength
(MPa)
75.0

Increase %

Fig. 4. The fracture surfaces of sample P and NS.

were still many nanometer scale pores and cracks in the CSH gel
that has negative effect on the strength and durability of specimens. As shown in Fig. 5(c), little connection was found between
the hydration products.
As shown in Fig. 6, the microstructure of mixtures NS-3 at
different curing time was uniform and compact. This may be
explained as follows: on the one hand, if nano-SiO2 particles are

uniformly dispersed in the mortar, they provide a nucleus for the

growth of hydration products in their vicinity due to high surface
energy. The increase of compressive strength greatly contributes
to strengthening the microstructure of hydration products for mortar containing nano-SiO2; on the other hand, nano-SiO2 is expected
to fill the void space and react with cement hydration products,
which compose multiphase material.

J. Liu et al. / Construction and Building Materials 101 (2015) 892901

897

mixing processes improved the homogeneity of the nano-SiO2

effectively, some agglomerated nano-SiO2 particles still existed.
The agglomeration was concentrated in the middle region, as
shown in Fig. 6(d). Such agglomerated nano-SiO2 will create weak
zones by pores and sometimes even deteriorated material
properties remarkably. Previous studies have shown that excessive
nano-SiO2 content did not improve strength, and different levels of
added nano-SiO2 seriously affect the flow ability of mortar, as
shown in Fig. 4, some visible holes were present on fractured
surfaces when the addition was very high.
Based on existing researches, it was significantly confirmed that
nano-TiO2 cannot react with Portland cement and water, but early
age hydration could be accelerated by nano-TiO2 which also
increase hydration degree of Portland cement [18,21,22]. SEM
micrographs of NT-4 mix of 28 days curing samples were shown
in Fig. 7(a) and (b). It was noticeable that, with increasing nanoTiO2 content, the matrix of NT-4 became more compact and uniform
because of nanoparticles filling effect. However, comparing with
nano-SiO2, nano-TiO2 has less effect on the improvement of mortar
strength. Fig. 7(c) and (d) showed SEM micrographs of NA-3 specimens containing 0.75 wt% nano-Al2O3 particles. As seen in Fig. 7
(c), the nano-Al2O3 additive particles were mainly around the C
SH gel and CAS (calcium aluminum silicate) gel. In Fig. 7(d),
however, many CH and AFt crystals formed and interspersed among
hydration products which imply that the pozzolanic reactions
between nano-Al2O3 and CH were topochemical. Although nanoAl2O3 could be filled in the pores of hydration products by Van der
Waals forces which improved the microstructure of the mortar,
large pores and cracks can be easily observed in the sample with
high nano-Al2O3 addition. Therefore, poor nanoparticles dispersion
and agglomeration affected the microstructure of the composites.
Fig. 7(e) and (f) were microscopic image of the mortar with
2.0 wt% of nano-ZnO, where the main constituents of the cement
mortar were unhydrated cement particles, AFt and little CSH
gel. It has been known that CSH gel is the main binding phase
which is essentially responsible for the strength of mortar, but lots
of unhydrated cement particles are observed in sample NZ-4. In
addition, CSH gel existed in isolation, and many needlehydrates were formed on the surface of cement particles in these
two pictures. With curing age increasing, larger holes still existed
in the hydration products as shown in Fig. 7(f). As a consequence,
nano-ZnO impeded the growth of cement hydration, especially at
early age. That means higher addition of ZnO nanoparticles could
lead to faster decrease of strength.
3.4. XRD analysis
As shown in Fig. 8, XRD was performed on the P, NS-4, NT-4,
NA-2 and NZ-3 samples. It can be observed that some significant
peaks are appeared in the results which indicate that large quantities of crystalline hydration products have changed in this reaction.
Compared with the control samples, the content of SiO2 and Ca
(OH)2 were reduced. It is because nano-SiO2 has high surface
energy which could react with Ca(OH)2 as follows [8]:
Fig. 5. SEM micrographs of P specimens at (a) 3 days, (b) 7 days and (c) 28 days of
curing.

Generally speaking, the interfacial transition zone (ITZ) surrounding the aggregate is the weak part of the matrix due to the
high watercement ratio. Fig. 6(c) shows the microstructure of
the ITZ between aggregate and the cement paste, and the ITZ
appears to be dense. The improvement in the ITZ microstructure
was probably due to the reaction between nano-SiO2 and calcium
hydroxide (CH) which combined some water in their products and
reduced the porosity of ITZ. Although the pre-dispersion and

BSiA H  OH ! BSiAOH quickly

BSiA OH ! BSiAOH quickly

BSiA CaOH2 ! CSH slow

Nano-SiO2 can be used as a filler to make the mortar internal
structure denser, and improve the interface transition zone [23].
As nano-SiO2 had high activity and can react with the Ca(OH)2
quickly, CSH gel was generated with high strength. In the early
reaction, nano-SiO2 with calcium hydroxide produced a rapid
initial hydration reaction. Compared with P, more CSH gel generated in this reaction explained the mortar with nano-SiO2 had

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J. Liu et al. / Construction and Building Materials 101 (2015) 892901

Fig. 6. SEM micrographs of NS-3 specimens at (a) 3 days, (b) 7 days and (c, d) 28 days of curing.

greater strength at early age (3 and 7 days). The hydration reaction

will stop when the relative humidity inside the mortar fell below a
critical value [24]. Because of the large specific surface area, nanoSiO2 can absorb a lot of surface water which will reduce the degree
of hydration. Therefore, the mixing amount of nano-SiO2 plays an
important role in the mortar.
As shown in Fig. 8, when comparing the peak values of hydration
products with 0% (P) and 0.5 wt% nano-Al2O3 (NA-2), the latter displayed a higher amount of hydration products which mean more C
SH gel and calcium aluminate hydrate (CAH) gel were generated
in the reaction. As a consequence, nano-Al2O3 changed the hydration products of the samples. Nano-ZnO could affect the setting time
and strength at early ages significantly. The hydration degree of
cement mortar containing 1.5 wt% nano-ZnO particles was lower
than that of the control at 28 days. This fact may be associated to
the reaction between nano-ZnO and Ca(OH)2 as follow [25]:

2ZnO CaOH2 4H2 O ! CaZnOH3 H2 O2

This reaction produce a surface layer of Ca(Zn(OH)3H2O)2 which

prevent transport of water to C3S phase and retard the setting.
4. Discussion
It is important to understand how nanoparticles affect the
hydration process of cement. Generally, nanoparticles can not only

fill the voids of the CHS structure leading to denser concrete, but
also act as nucleation centers contributing to the development of
the cement hydration. According to former literatures
[8,9,11,29,30], NS was found to be much more efficient than traditional mineral additives for improving the strength, durability and
permeability of cement-based materials. The sketch maps of the
hydration process of traditional and nano-engineered concrete
are shown in Fig. 9. When NS particles were added to cement
2+
grains, H2SiO2
which
4 formed and reacted with the available Ca
formed an additional CSH and these CSH particles served as
seeds for the formation of more compact CSH phase [26]. Moreover, the degree of density of ITZ was closely related to the
strength of composites, while there exist more pores, crystal in this
zone easily crack, compare with the cement matrix, load cannot
effectively transform to matrix [15]. In this experiment, the compressive strength of specimen was increased by 13.2%, 9.5% and
7.5% at 3, 7, 28 days respectively when the proportion of NS up
to 2.0 wt% (Table 4). In addition, a great deal of CSH gels was
produced due to the addition of nano-SiO2, and it filled the voids
to improve the density of ITZ and binding paste matrix (Fig. 6
(c)). Thus, the early and long-term mechanical properties of
cement composites were improved.
The strength of the nanoparticles modified cement composite
was also influenced by the effective dispersion of nanoparticles.
With good dispersion, addition of NS will act as fillers to occupy
the void space among cement hydrations and improve the

J. Liu et al. / Construction and Building Materials 101 (2015) 892901

899

Fig. 7. SEM micrographs of (a, b) NT-4 specimens, (c, d) NA-3 and (f) NZ-4 at 28 days, and (e) NZ-4 at 7 days of curing.

microstructure of the cement composites. Unfortunately, some

agglomerated nanoparticles still existed in the matrix even though
the pre-dispersion and mixing processes were used to improve the
homogeneity of the nanoparticles. However, the agglomerates in
nanoparticles possess a high water adsorption due to their high
surface area and high nano-scale porosity [27]. As shown in
Fig. 6(d), agglomerated NS will create weak zones by pores and

sometimes even deteriorated material properties remarkably. This

study revealed that, without sufficient superplasticizer additives,
the aggregation of NS and NA particles was formed instantaneously, and the amount of agglomerates increased with increasing nanoparticles concentration. Therefore, poor dispersion of
nanoparticles leads to several defects in the nanocomposites and
decreases the reinforcing effect of nanoparticles.

900

J. Liu et al. / Construction and Building Materials 101 (2015) 892901

Table 5 summarized current knowledge on the field of cement

composites containing nanoparticles. Based on the data in this
table, contradictory results were obtained from previous studies
conducted on the optimal nanoparticle proportions that yield the
best experiment results concerning the mechanical properties of
cement-based composites. For instance, Jo et al. [6] found that
the proper proportion of NS addition was as high as 10%, but some
authors [2,3] found that this ratio should vary between 1% and 5%.
Similarly, the optimum NA content was still different from one
author to another, but 12% seemed to be the optimum. It is difficult to compare the results derived from the different parameters
of concrete mix proportion, but these experiment results suggest
that the role of nanoparticles on fluidity reduction is more than
traditional mineral additives and it is developing by increasing
the specific surface area (SSA) of the particles. That means the
higher SAA of nanoparticles, the greater reduction of fluidity.
Usually, researchers recommended control over the water and

Fig. 8. XRD of different group of mortar.

Fig. 9. Scheme diagram of traditional and nanoengineered concrete hydration process.

Table 5
Enhancement of nanoparticles to compressive strength of cementitious composites.
Type

Matrix

Specific surface area

(m2/g)

Optimal proportions
(wt%)

Water/binder
ratio

Water reducing agent

(binder wt%)

28-day compressive strength

increase %

References

NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NA
NA
NA
NA
NA
NT
NT
NT
NT
NT

Mortar
Paste
Mortar
Paste
Mortar
Concrete
Mortar
Mortar
Paste
Mortar
Mortar
Mortar
Concrete
Concrete
Concrete
Mortar
Mortar
Paste
Mortar
Mortar

60
90
90
160
160 20
160 20
200
220 3
345
640 50
10 5
100 15
163 20
163 20

5080
58.8

240

10.0
3.0
7.0
3.0
11.0
4.0
1.25
2
3.8
4.0
7.0
1.25
3.0
1.5
1.5
5
0.5
10
5
1.5

0.5
0.485
0.485
0.22
0.5
0.4
0.4
0.29
0.5
0.28
0.4
0.4
0.4
0.4
0.25
0.45
0.29
0.35
0.4
0.35

2.9
0.65
1.3
0.25
5.6
1
0.75
1
1
2
0
0.75
1
0
1.5
0.5
1
0

1.6

166.0
54.3
13.1
23.0
26.0
74.4
19.2
7.5
17.1
39.3
1.8
4.3
117
16.3
55.0
15
0.8
25.6
20
19

[6]
[29]
[29]
[8]
[30]
[11]
[31]
This study
[32]
[28]
[15]
[33]
[10]
[34]
[35]
[36]
This study
[37]
[38]
[39]

J. Liu et al. / Construction and Building Materials 101 (2015) 892901

superplasticizer content, otherwise high quantity utilization of

nanoparticles will reduce the strength instead of improving [26].
For one thing, it can be seen from the table that increasing SSA
and the dosage of NS in cement composites leads to a decrease
of optimal proportions of nanoparticles. For particle SSA higher
than 200 m2/g, proper proportion of NS addition is less than 5%.
On the other hand, in specimens with same SSA and w/c [29], water
reducing agent increases with the optimal proportions of NS percentage. Thereby, through determining reasonably parameters
about the content of nanoparticles, w/b and superplasticizer dose
level, good strengthening effect can be achieved.
5. Conclusions
In this work, four kinds of nanoparticles, nano-SiO2, nano-Al2O3,
nano-TiO2 and nano-ZnO, have been selected to study the mechanical and microstructure of nano-composites. The results demonstrated that nanoparticles can be used in cement-based materials
to alter different properties, such as strength, hydration rate and
setting time.
Excessive amount of nanoparticles results in particle agglomeration and decrease of fluidity. Moreover, the optimum content of
nanoparticles for cementitious materials depends on the average
particle size of nanoparticles which can be expressed in terms of
surface area to mass ratio.Nano-TiO2 and nano-ZnO have little
effect on the mortar fluidity due to their lower specific surface
area. On the contrary, the flow loss continuously decreased with
the increase amount of nano-SiO2 and nano-Al2O3.
Nano-SiO2 could make microstructure of harden paste solider
dense and accelerate the cement hydration process, also, the
mechanical strength of mortar was improved at different ages.
The compressive and flexural strength of mortar specimens
increased by using nano-SiO2 particles, but overuse of nano-SiO2
result in performance degradation. The optimum content of
nano-SiO2 in mortar was 3.0 wt% in this study. However, the compressive and flexural strength of the specimens slightly decreased
when the mortar containing nano-Al2O3 and nano-TiO2 particles,
and it is seen to be more significant at later age (28 days).
The strength of nano-ZnO modified mortar was decreased with
higher nano-ZnO particles addition, and 2.0 wt% content resulted
in 80% decrease in compressive strength compared to the control
at 28 days.
Acknowledgement
Support from National Key Technology Research and Development Program of the Ministry of Science and Technology of China
(No. 2012BAJ13B04) is gratefully acknowledged.
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