Construction and Building Materials 205 (2019) 245–256

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Construction and Building Materials

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

Effect of nano-clay de-agglomeration on mechanical properties

of concrete
Nehal Hamed a, M.S. El-Feky b, Mohamed Kohail a,⇑, El-Sayed A.R. Nasr a
a
Structural Engineering Department, Ain Shams University, Cairo, Egypt
b
Department of Civil Engineering, National Research Centre, Cairo, Egypt

h i g h l i g h t s

Investigate the effect of nano-clay de-agglomeration on concrete properties.

The optimum percentage of dispersed nano-clay particle was recommended.

Studying the effect of dispersed nano-clay on the concrete microstructure.

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

Article history: This paper investigates the effect of nano-clay dispersion on concrete properties. This was extensively
Received 18 September 2018 studied by using various percentages of nano-clay (5, 7.5, and 10%) as cement partial replacements by
Received in revised form 1 February 2019 two ways; added as-received, added after being dispersed in water by using bath sonicator. The evalua-
Accepted 4 February 2019
tion was based on the compressive strength, split tensile strength, flexural strength, slipping bond
strength, and split bond strength of nano-clay concrete and the microstructure analysis was verified
by SEM, XRD, and AFM examinations. The test results revealed that the sonication of nano-clay particles
Keywords:
significantly enhanced concrete properties when compared to those of as-received nano-clay concrete.
Nano-clay
Sonication
The optimum percentage for cement substitution by Nano-clay was found to be 7.5% for both; the as-
De-agglomeration received, and the sonicated nano-clay. The presence of NC particles resulted in dense and well-
Mechanical properties compacted matrix than that of the control mix as has shown in the SEM micrographs, the XRD and
Microstructural analysis AFM results indicated the higher reactivity of the sonicated NC than the as-received NC.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction
Concrete is one of the most important and common materials in
the construction industry, Lately, many researchers have con-
ducted deep studies to improve the environmental friendliness of
concrete to make it suitable to be one of the green building mate-
rials [1–5], the most successful researches in this regard is the use
of pozzolanic materials like fly ash, silica fume, and metakaolin as
partial substitutes for cement resulting in reducing the cement
content significantly in addition they also proved their efficiency
in promoting the mechanical properties of concrete beside their
friendly environment effects [5–14].
Recently, the applications of nanotechnology have become
more widespread in the construction field [15], Nanotechnology
is defined as the restructuring of materials to be in nano-size (less
⇑ Corresponding author.
E-mail address: m.kohail@eng.asu.edu.eg (M. Kohail).
than 150 nm) for developing new properties and functions [16].
The use of nanomaterials as partial substitutes for cement in con-
crete can improve its properties due to the presence of their parti-
cles in nano-size [17], and since the main hydration product of
cement-based materials is C-S-H gel, is a nanostructured material
[18], in addition, a number of widely spread nano-sized pores exist
in the cement matrices, that make concrete a micromaterial influ-
enced by its nano-properties.
Nanomaterials can be classified into two categories; pozzolanic
as the case of (nano-silica, nano-alumina, nano-clay), and fiber like
as for (carbon nanotubes and carbon nano-fiber). pozzolanic mate-
rials are characterized by their pozzolanic reactions which react
with CH producing additional C-S-H gel leading to enhancing the
matrices strengths [19–24], while fiber-like materials are charac-
terized by their needle action systems due to their shapes, that
could bridge the cracks and resist the propagation of cracks leading
to enhancing the tensile properties of the matrix [21,22,25,26].
Nano-clay (NC) is one of the nanomaterials which researchers
had focused on studying its effect on the performance of cement

https://doi.org/10.1016/j.conbuildmat.2019.02.018
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
246 N. Hamed et al. / Construction and Building Materials 205 (2019) 245–256

mortars and concretes, recently that combines both characteristics

of the nanomateraials. NC showed high pozzolanic reactivity and
its particles shape which is flaky, elongated, thin, and platy which
can provide the needle action system [27–36]. There are some
investigations studied the effect of NC replacement on the proper-
ties of concrete (compressive, tensile, and flexural strengths) [28–
36]. However, in these studies, there were clear contradictions in
determining the optimum percentage of NC replacement. Although
some authors [30–33,35,36] reported that the optimum percentage
of NC has to be 1% or less due to agglomeration caused by difficul-
ties to disperse the particles during mix, others [29,34–36] stated
that the enhancement of concrete properties could be directly pro-
portional to the percentage of NC up to 10%. Some authors
[30,33,36] attributed this variation to the poor dispersion of NC
particles, which lead to the formation of NC agglomerations around
grains of cement and hinders the hydration process of cement
resulting in weak zones within the matrix.
Considering the previous studies about the agglomeration prob-
lem of nanoparticles that have a strong tendency to assemble
around each other and form agglomerations as a result of van
Fig. 1. TEM of NC particles.
der Waals force [37], the formation of these agglomerations found
to affect negatively the performance of concrete matrix [21,23,37–
39], as such, and in order to solve the nanoparticles agglomeration mixtures aggregates consist of an incorporation of fine sand and
problem, an effective dispersion technique should be used, authors crushed dolomite with the percentage of 35% and 65% by weight
previously used various dispersion techniques such as; stirring, respectively. The used high range water reducer (Type G superplas-
homogenizing and sonicating to disperse different types of ticizer) is used. It is an aqueous solution of modified
nanoparticles [24,25,38–41], the sonication proved to be the most polycarboxylates.
effective technique for dispersing nanoparticles in aqueous solu-
tions, as previously reported by [23,38–42], however, there is no
2.2. Mix design proportions
literature found studying the effect of NC de-agglomeration on
concrete properties.
In this study, seven concrete mixes were designed, control mix
The aim of this research plan is to investigate the effect of NC
is made of natural aggregates, cement, water, and superplasticizer
particles before and after de-agglomeration on the mechanical
(S.P), while the NC mixes are made in the same manner but by sub-
properties of concrete and to determine the optimum NC percent-
stituting cement with different percentages of NC particles (5%,
age to improve the performance of concrete, the outcome of this
7.5%, and 10%) by two ways; (a) using as-received NC, and (b) using
research program will help not only in enhancing the concrete
NC after being sonicated in equal amount of water using indirect
properties but also in reducing the cement quantities, and the NC
bath sonicator to help dispersing its particles and decrease the for-
quantities to be used. The reduction in the quantities of these
mation of NC agglomerations [38]. A modern ultra-sonication bath
materials will definitely reduce the CO2 footprint and increase
is used for NC particles dispersion with constant time, power, and
the environmental impact of the utilized NC particles. Concrete
frequency of 5 min, 135 W, and 40 kHz respectively. The water to
will be examined concerning the air content, compressive strength,
binder ratio is set to a steady value of 0.43 for all mixes. The mix
split tensile strength, flexural strength, and bond strength with its
proportions of NC concrete mixes (kg) per 1 m3 are shown in
two behaviors of slipping and split. Also, the microstructural anal-
Table 2.
ysis of hardened concrete will be verified by scanning electron
microscope (SEM) test, X-ray Diffraction (XRD) test and Atomic
2.3. Mixing procedure
Force Microscope (AFM).
All concrete mixes are prepared by dry mixing the coarse aggre-
2. Experimental program gates, fine aggregates, and cement in a concrete turn-tilt mixer for
1.5 min, then adding NC particles after blending in a part of the
2.1. Materials mixing water for all the as-received NC mixes or after being soni-
cated in a part of mixing water for all the sonicated NC mixes, and
Ordinary Portland Cement (OPC) used in this research was (CEM then mixing for another 1 min, and finally, adding the superplasti-
I/42.5R) in accordance with ASTM C150 [43]. NC used in this cizer with the rest of the mixing water and mixing for another
research was an off-white powder. Table 1 show the chemical 1 min.
composition of used NC and Fig. 1 shows the TEM of NC. Natural
sand is used as fine aggregates with particles size below 0.5 mm, 2.4. Preparation of the specimens, curing and tests
specific gravity of 2.58 g/cm3, and fineness modulus of 2.25.
Crushed clean dolomite is used as coarse aggregate of the maxi- Evaluation of the used dispersion technique was applied on 5%
mum size of 12 mm and specific gravity of 2.96 g/cm3. The NC using the Mastersizer 3000 laser diffraction particle size

Table 1
The chemical composition of used Nano-clay.

Element SiO2 Fe2O3 Al2O3 CaO MgO TiO2 Na2O L.O.I

Content % 61.24 1.06 20.89 0.16 0.22 1.61 0.71 14.11
 N. Hamed et al. / Construction and Building Materials 205 (2019) 245–256 247

Table 2
Mixes components (kg) per 1 m3.

Concrete mix (ID) Cement (kg/m3) Aggregates (kg/m3) Water (kg/m3) SP (kg/m3) NC (kg/m3) Dispersion technique
Co 450 1706 192 2.7 – –
5% NC 427.5 1706 192 2.7 22.5 Stirred by the wooden stick with water
7.5% NC 416.25 1706 192 2.7 33.75
10% NC 405 1706 192 2.7 45
5% SNC 427.5 1706 192 2.7 22.5 5 min sonication
7.5% SNC 416.25 1706 192 2.7 33.75
10% SNC 405 1706 192 2.7 45

analyzer. Once the concrete mixing process was finished, air con-
tent test was performed on the fresh concrete according to ASTM
C231 [44]. Cubes of (100  100  100) mm3 were prepared and
cast for implementing compressive strength test after 7 and
28 days of water curing according to BS EN 12390-3 [45]. Cylinders
of (100 mm diameter and 200 mm in height) were prepared and
cast for implementing split tensile strength test after 28 days of
water curing according to ASTM C496 [46]. Prisms
(50  50  200) mm3 were prepared and cast for implementing
the flexural strength test after 28 days of water curing according
to ASTM C293 [47]. Cubes of (150  150  150) mm were prepared
and cast for implementing the bond strength test after 28 days of
water curing for steel re-bar of diameter of 12 mm and 16 mm
according to RILEM 7-II-128 [48]. In order to investigate the effect
of the presence of NC particles on the bond strength modes of fail-
ure, a 75 mm length of polyvinyl chloride tubing is used to de-bond
the steel bar rooted inside the specimen. This makes the bond slid-
ing failure dominates over other types of failure as like yielding of
steel reinforcement, Fig. 2 shows a schematic of the pullout test
specimen. For all tests, three samples were prepared for each test
and the result of the test was the average results for them. Finally,
three chosen samples of concrete representing the optimum per-
centage of as-received NC, sonicated NC, and the control mixes
were examined after 56 days of water curing to study the
microstructural analysis by Scanning electron microscope (SEM)
test, and X-ray Diffraction (XRD) test, as for the Atomic Force
Microscope (AFM), three pastes samples representing the optimum
percentage of as-received NC, sonicated NC, and the control mixes
were prepared and examined after 28 days of water curing.
3. Results and discussion
3.1. Evaluation of used dispersion techniques
Fig. 3 shows the Particles size distributions (P.S.D) for both; the
as-received, and the sonicated NC with a concentration similar to
the used in the concrete pouring process. For as-received NC, the
surface area was 30.55 m2/kg and average particle size was
204 mm (size of agglomerations), while for sonicated NC, the sur-
face area was 51050 m2/kg and average size particle was 0.13 mm
(size of agglomerations).
The significant increase in the surface area, as well as, the signif-
icant reduction in the average particle size of NC after being soni-
cated can be attributed to the efficiency of ultra-sonication in
breaking down the large agglomerates of NC particles into smaller
agglomerates or even primary particles as compared to as-received
NC.
3.2. Air content
Fig. 4 shows the air content percentages of both; as-received
and sonicated NC concrete. Generally, cement substitutions by
either; the as-received or sonicated decreased the air content per-
centages for all concrete mixes when compared to the control mix
(without NC).
The decreases in air content percentages were 5.6%, 11.1%, and
8.3% for cement substitution percentages of 5%, 7.5%, and 10% by
as-received NC respectively. As for sonicated NC mixes, the
enhancements reached 11.1%, 19.4%, and 16.7% as compared to
the Co mix.
The slight decrease in air content with as-received NC can be
attributed to the poor dispersion of NC particles and the forming
of large agglomerates which push the cement particles away from

20
19
Sonicated NC 18
17
As-received NC
16
15
Volume Density (%)

14
13
12
11
10
9
8
7
6
5
4
3
2
1
0
0.01 0.1 1 10 100 1000
Size Classes (µm)

Fig. 2. Schematic of pullout test specimen. Fig. 3. P.S.D of both; as-received NC, and sonicated NC.
248 N. Hamed et al. / Construction and Building Materials 205 (2019) 245–256
Fig. 4. Air content percentages of both; as-received and Sonicated NC concrete
mixes.
each other resulting in increasing the solid spaces, and conse-
quently increase the air content relative to Sonicated NC, in addi-
tion to the air spaces already within the agglomerates.
The significant decrease in air content with Sonicated NC can be
attributed to the influence of the ultra-sonication which breaks
down the agglomerates into smaller agglomerates or even into sin-
gly dispersed particles and also reduce the initial particles size,
leading to increasing its ability in acting like filler to the nanopores
of concrete matrix, and therefore, reduce the formation of air
spaces in concrete matrix relative to as-received NC.
Relative to as-received NC mixes, the air content decreased by
5.9%, 9.4%, and 9.1% for 5%, 7.5%, and 10% Sonicated NC respec-
tively. This indicates to the efficiency of the ultra-sonication
method for dispersing NC particles, de-agglomeration and ultrafine
the NC particles due to the inter-particle collision.
3.3. Compressive strength
Figs. 5 and 6 show the compressive strength results of as-
received NC and Sonicated NC concrete mixes. The cubes tested
after 7 days of water curing will be referred to as 7 days compres-
sive strength while those tested after 28 days of water curing will
be referred to as 28 days compressive strength. Generally, cement
substitution by either; the as-received NC, or Sonicated NC
enhanced the early (7 days), and late (28 days) ages compressive
strengths for all concrete mixes.
Fig. 5. Compressive strength of both; as-received and Sonicated NC concrete mixes
after 7 days of curing.
Fig. 6. Compressive strength of both; as-received and Sonicated NC concrete mixes
after 28 days of curing.
At 7 days, the highest compressive strength reached 33.0 MPa
for the cement substitution by 7.5% as-received NC, while the high-
est compressive strength reached 41.2 MPa for the cement substi-
tution by 7.5% Sonicated NC rather than 26.5 MPa for the control
mix.
The enhancements in 7 days compressive strength for cement
substitution percentages of 5%, 7.5%, and 10% by as-received NC
were 18.87%, 24.52%, and 7.55% as compared to the Co mix respec-
tively, while for Sonicated mixes, the enhancements reached
40.75%, 55.47%, and 26.04% as compared to the Co mix
respectively.
At 28 days, the highest compressive strength reached 44.6 MPa
for the cement substitution by 7.5% as-received NC, while the high-
est compressive strength at age of 28 days reached 57.2 MPa for
the cement substitution by 7.5% Sonicated NC rather than
37.7 MPa for the control mix.
The enhancements in 28 days compressive strength for cement
substitution percentages of 5%, 7.5%, and 10% by as-received NC
were 2.65%, 18.3%, and 9.81% as compared to the Co mix respec-
tively, as for Sonicated NC mixes, the enhancements reached
16.45%, 51.72%, and 43.24% as compared to Co mix respectively.
The compressive strength at the early, and the late ages were
enhanced with increasing the cement substitution percentages
by either; the as-received or the Sonicated NC up to 7.5%, and then,
it was reduced with the use of 10% NC substitution, noticing that
the 10% NC substitution was still higher than the Co mix. This could
be possibly due to van der Waals force where increasing the num-
ber of NC particles, increased their ability to assemble around each
other and form agglomerations without any chemical interactions
within concrete mixes. These agglomerations form non-hydrated
spots which weaken the bond among cement and aggregates,
and therefore, reduce the compressive strength of concrete.
When compared to as-received NC mixes, the enhancements of
compressive strength for 7 days reached (18.41%, 24.85%, and
17.19%), whereas for 28 days reached (13.44%, 28.25%, and
30.43%) for the cement substitution percentages of 5%, 7.5%, and
10% Sonicated NC respectively. This can be attributed to the influ-
ence of ultra-sonication in breaking down the agglomerates into
smaller agglomerates or even into singly dispersed particles.
For the cement substitution by (5% and 7.5%) Sonicated NC, the
compressive strength enhanced significantly at the early age rela-
tive to that of the Co mix. This can be attributed to; (1) the filling
effect of NC particles due to its nano-size which fills the existing
pores in concrete matrix and makes the matrix be well compacted,
denser and uniformly restructured [30–36,49–52], (2) The high
pozzolanic reactivity of NC particles which reacts with excess CH
 N. Hamed et al. / Construction and Building Materials 205 (2019) 245–256
forming extra C-S-H gel which enhances the ITZ among aggregates
and cement blends resulting in promoting strengths [30–
36,49,51,53], (3) NC particles acting like a nucleus for cement
hydration gels which led to forming reinforced C-S-H
[32,33,36,54], while for 10% cement substitution by Sonicated
NC, the slight enhancement of 28 days compressive strength was
thought to be due to high particle concentration at using a steady
volume of water. The high concentration results in increasing the
inter-particles collision during the sonication process, whenever
NC particles collide, they merge together and increase the forming
of NC agglomerates. These agglomerates had low reactivity and
require a prolonged time than 28 days to supplement pozzolanic
reaction and react with the CH to form extra C-S-H gel and to
improve the concrete strength. However, these agglomerates can
still fill part of the pores within the matrix resulting in the
much-compacted matrix.
The compressive strength ratios of 7 days to 28 days reached
(81.4% and 74%) and (85% and 72%) for (5% and 7.5%) cement sub-
stitutions by both as-received and Sonicated NC respectively, this
indicates the well dispersion of small NC particles concentrations
at steady volume of water.
3.4. Split tensile strength
Fig. 7 shows the split tensile strength results of both; the as-
received NC, and the Sonicated NC concrete. Generally, the cement
substitution by either; as-received or Sonicated NC enhanced split
tensile strength at 28 days for all concrete mixes. The split tensile
strength results showed the same trend as the results of compres-
sive strength.
The highest split tensile strength reached 3.6 MPa for 7.5%
cement substitution by as-received NC, while for 7.5% Sonicated
NC reached 4.2 MPa rather than 3.28 MPa for the control mix.
The enhancements in split tensile strength were 2.74%, 9.76%,
and 4.88% for cement substitution percentages of 5%, 7.5%,
and10% by as-received NC respectively, as for Sonicated NC mixes,
the enhancements reached 10.67%, 28.05%, and 17.38% as com-
pared to the Co mix. The split tensile strength enhancement for
cement substitution by NC can be attributed directly to the needle
action system of the NC particles as a result of the NC particles
shape which is flaky, elongated, thin, and platy [33]. When tensile
cracks occur in the matrix, NC platelets may inhibit and limit the
propagation of the tensile micro-cracks. This performance could
be seen lately in the SEM micrographs, and it was also previously
referred to by Hosseini et al. [33,55]. In addition to that, the filling
effect, the high pozzolanic reactivity, and nucleation effects of NC
Fig. 7. Tensile strength of both; as-received and Sonicated NC concrete mixes after
28 days of water curing.
249
particles which improved the compressive strength, and conse-
quently affected the enhancement of the concrete tensile strength.
Relative to as-received NC mixes, the split tensile strength
enhancements at 28 days reached 7.72%, 16.67%, and 11.92% for
cement substitution percentages of 5%, 7.5%, and10% by Sonicated
NC mixes respectively. The difference in the performance between
the as-received NC and the Sonicated NC particles can be attributed
to the effectiveness of ultra-sonication in dispersing NC particles,
breaking the NC agglomerates resulting in ultrafine and high reac-
tivity NC particles that in turn leading to increase the efficiency of
NC particles regarding to the pozzolanic reactivity, nano-filling,
and reinforcing the concrete matrix, and consequently, enhance
the tensile strength relative to as-received NC.
3.5. Flexural strength
Fig. 8 shows the flexural strength results of both; the as-
received and the Sonicated NC concrete mixes. In general, the
cement substitution by either; as-received or Sonicated NC
enhanced flexural strength at 28 days for all concrete mixes. Flex-
ural strength results showed the same trend as the results of the
compressive and split tensile strengths.
The highest flexural strength reached 10.75 MPa and 12.62 MPa
for 7.5% cement substitution by as-received and Sonicated NC
respectively rather than 9.35 MPa for the Co mix, the enhance-
ments of the flexural strength reached 14.97% and 34.97% respec-
tively as compared to the control mix.
The flexural strength enhancements were 5%, 15%, and 10% for
cement substitution percentages of 5%, 7.5%, and10% by as-
received NC respectively, as for Sonicated NC mixes the flexural
strength enhancements reached 15%, 35%, and 25.13% relative to
the Co mix respectively.
The addition of 5% Sonicated NC had the same gain in flexural
strength to the addition of 7.5% as-received NC. This indicates
the efficiency of the ultra-sonication in dispersing the NC particles
and breaking down the NC agglomerations resulting in forming
arranged arrays in the cement based matrix as mentioned by He
& Shi et al. [50], Hosseini et al. [51], and Hosseini & Vaziri et al.
[55], such arranged arrays introduce a microstructural regularity
into the concrete matrix via a more stable bonding framework
[51], In addition, the ultra-sonication increased the ability of NC
particles in; (1) acting like filler to the nanopores of concrete
matrix, (2) increasing reactivity of NC particles which reacts with
CH and produce an extra C-S-H gel, and (3) increasing the nucle-
ation effect of NC particles leading to reinforcing the cement
hydration, and consequently, enhance the flexural strength relative
to as-received NC mixes.
Fig. 8. Flexural strength of both; as-received and Sonicated NC concrete mixes after
28 days of water curing.
250 N. Hamed et al. / Construction and Building Materials 205 (2019) 245–256

When comparing the flexural strength results of Sonicated with

as-received NC mixes results, it was found that the flexural
strengths with the Sonicated NC mixes were enhanced by 9.5%,
17.4%, and 13.76% for cement substitution percentages of 5%,
7.5%, and 10% respectively relative to those of as-received NC
mixes.

3.6. Bond strength

As per RILEM 7-II-128, Concrete cover affects whichever behav-

ior of the bond strength will prevail. If there is enough concrete
cover around the bar (more than 4.5 the rebar diameter), the slip-
page behavior will occur. While in the absence of enough concrete
cover (less than 4.5 the rebar diameter), the split behavior will
occur [48].
Although adhesion and friction are present when a deformed Fig. 10. Relation between 28 days compressive and 12 mm rebar bond strengths of
bar is loaded for the first time, these bond-transfer mechanisms as-received NC concrete mixes.
are quickly lost, leaving the bond to be transferred by bearing on
the deformations of the bar. Equal and opposite bearing stresses
act on the concrete. The forces on the concrete have both a longi-
tudinal and a radial component. The latter causes circumferential
tensile stresses in the concrete around the bar. Eventually, the con-
crete will split parallel to the bar, and the resulting crack will prop-
agate out to the surface of the beam. The split cracks follow the
reinforcing bars along the bottom or side surfaces of the beam, a
slippage failure occurs, where the bar and the annulus of concrete
between successive deformations pull out along a cylindrical fail-
ure surface joining the tips of the deformations [56], as it was con-
firmed by Torre-Casanova et al. [57] who presented equations for
distinguishing split failure as a function of the tensile properties
of concrete and for distinguishing slippage failure as a function
of the compressive properties of concrete, and good agreement
with M.S. El-Feky et al. [58], and N. Hamed et al. [59].

3.6.1. Rebar-12 mm
Figs. 9–11 show the bond strength results of both; the as-
received and the Sonicated NC concrete mixes. Generally, for
12 mm re-bars specimens, the concrete cover was more than 4.5
the rebar diameter, so there were enough concrete covers and
the slippage was the dominant behavior [48,56,58,59].
The slippage performance is directly affected by the compres-
sive strength of the concrete mix, as such, the bond strength per-
formance of 12 mm specimens followed the same trend of the
compressive strength [57–59].
Fig. 11. Relation between 28 days compressive and 12 mm rebar bond strengths of
Sonicated NC concrete mixes.
The highest bond strength reached 23.34 MPa and 29.62 MPa
for 7.5% cement substitution by as-received and the Sonicated NC
respectively rather than 19.1 MPa for the control mix, the enhance-
ments of the bond strength reached 22.21% and 55.08% respec-
tively as compared to the control mix.
The enhancements in bond strength were 5.55%, 22.21%, and
21.66% for cement substitution percentages of 5%, 7.5%, and 10%
by ANC respectively, as for Sonicated mixes the bond strength
enhancements reached 15.27%, 55.08%, and 42% relative to Co mix.
When compared to the as-received NC mixes, the gains in the
bond strength with using 12 mm rebars reached (9.21%, 26.9%,
and 16.43%) for the cement substitution percentages of 5%, 7.5%,
and 10% by Sonicated NC respectively.

Fig. 9. Bond strength of both; the as-received and Sonicated NC concrete mixes
using 12 mm rebar after 28 days of water curing.
3.6.2. Rebar-16 mm
Figs. 12–14 show the bond strength results of both; the as-
received and the Sonicated NC concrete mixes when using
16 mm rebars. In general, the split behavior occurred for all speci-
mens of 16 mm diameter entrenched rebars in concrete (for either;
the Co mix, or mixes incorporating (as-received /Sonicated)
[48,56,58,59].
As per the previous discussion and since the split performance
is directly affected by the tensile strength of the concrete mix, so
the bond strength performance of 16 mm specimens followed the
same trend of the tensile strength. The highest bond strength
 N. Hamed et al. / Construction and Building Materials 205 (2019) 245–256
Fig. 12. Bond strength of both; the as-received and Sonicated NC concrete mixes
using 16 mm rebar after 28 days of water curing.
Fig. 13. Relation between 28 days Tensile and 16 mm rebar bond strengths of as-
received NC concrete mixes.
Fig. 14. Relation between 28 days tensile and 16 mm rebar bond strengths of
Sonicated NC concrete mixes.
reached 22.12 MPa for cement substitution by 7.5% as-received NC
rather than for 21.09 MPa for Co mix (without NC).
The bond strengths enhancements were 1%, 4.88%, and 1.48%
for cement substitution percentages of 5%, 7.5%, and 10% by as-
251
received NC respectively, as for Sonicated NC mixes, the enhance-
ments reached 6.92%, 18.24%, and 13% respectively relative to Co
mix.
While as compared to the as-received NC mixes, the enhance-
ments in the bond strength when using 16 mm-rebar reached
(5.87%, 12.75%, and 11.36%) for the cement substitution percent-
ages of 5%, 7.5%, and 10% by Sonicated NC respectively.
For 12 mm rebars specimens, the concrete cover was more than
4.5 the rebar diameter, so there was enough concrete cover around
the rebar and the slippage was the dominant behavior, while for
16 mm rebars specimens, the concrete cover was less than 4.5
the rebar diameter, so there wasn’t enough concrete cover and
the split behavior was the dominant, the results are in a good
agreement with Torre-Casanova et al. [57], M.S. El-Feky et al.
[58], and N. Hamed et al. [59].
The improvements of bond strength with the cement substitu-
tions by either; the as-received or the Sonicated NC can be attrib-
uted to; (1) Pozzolanic Reactivity of NC particles resulting in
producing extra C-S-H gel which enhances the ITZ among aggre-
gates and cement blends, and also enhances the bond between
the steel rebar and concrete that in turn enhances the concrete
strengths, (2) NC particles are acting like nucleus for cement
hydration gels leading to forming reinforced C-S-H, (3) The filling
effect of NC particles which resulting in the well compacted, dense
and uniformly restructured matrix, and (4) needle effects of NC
particles.
The bond strength was improved when increasing the cement
substitution percentages by either; the as-received, or the Soni-
cated NC up to 7.5%, after that, it was decreased with 10% NC sub-
stitution, noticing that the 10% NC substitution was still higher
than the Co mix. This can be attributed to the van der Waals force
when adding a large percentage of NC particles, it assembles
around each other and forms relatively large agglomerations which
fail to act as filler to the nanopores within matrix and hindered its
pozzolanic reactivity resulting in weakening the ITZ between
aggregates and cement blends, and consequently, weaken the bond
between concrete and steel rebar, and therefore, reduce the bond
strength of concrete.
For 12 mm rebars, although the substitution by 7.5% Sonicated
NC is one and half times higher in content than 5% Sonicated NC,
the gain in bond strength for 7.5% NC (18.24%) reached 2.64 times
the gain in the bond strength for 5% NC (6.92%). As for 16 mm
rebars, the gain in bond strength by the substitution of 7.5% Soni-
cated NC (55.08%) reached 3.6 times the gain in the bond strength
of 5% Sonicated NC (15.27%).
3.7. Scanning electron microscopy (SEM)
Scanning Electron Microscope (SEM) images were taken to
study the micro-structure for the materials of three different spec-
imens showing the effect of NC presence before and after being
exposed to ultra-sonication relative to Co mix without NC
substitution.
Figs. 15–17 show the SEM micrographs for the Co, 7.5% as-
received NC, and 7.5% Sonicated NC mixes respectively, as for the
SEM plates representing the morphology and structure of the con-
trol sample relative to NC incorporated cement systems, the found
structures are highly identifying the reasons behind the previously
discussed mechanical properties, i.e. the Co mix showed much
weaker performance in most of the mechanical properties relative
to NC systems.
The ettringite needles, as well as the calcium hydroxide crystals,
can be easily identified in Co mix micrograph (Fig. 15a and b), in
addition to the existence of relatively large spread voids, moreover,
the CSH particles are discontinued, and interfering with the cal-
cium hydroxide crystals, and the ettringite needles resulting in
252 N. Hamed et al. / Construction and Building Materials 205 (2019) 245–256

Fig. 15. SEM micrograph of control mix for two different spots (a and b).

Fig. 16. SEM micrograph of 7.5% as-received NC mix for four different spots (a–d).

weak, highly fractured, inconsistent matrix as it can be seen in the
micrographs (Fig. 15b).
While for the NC micrographs, the presence of the NC particles
within cement matrix no matter sonicated or not, enhanced the
consistency and homogeneity of both mixes resulting in a more
compacted matrix (Figs. 16a and 17a). It can be easily recognized
from the NC micrographs that the presences of NC particles lead
to minimizing the void ratio within the matrix and results in a
more-dense matrix. This could be due to the previously discussed
filling effect where the clay nano particles fill all the nano-sized
pores, in addition to the reactivity of NC particles with the residual
CH from the cement hydration process resulting in a higher
amount of CSH gels (Figs. 16a and 17a).
From the as-received NC (7.5% as-received NC) micrographs,
although groups of unreacted small agglomerations of the NC
could be found, the matrix was still dense and compacted. These
small agglomerations where found surrounded by C-S-H in a con-
crete spot which illustrates the nucleation site effect of the NC par-
ticles in (Fig. 16c and d), the NC particles acting like a nucleus
where the cement hydration products gather around forming a
 N. Hamed et al. / Construction and Building Materials 205 (2019) 245–256 253

Fig. 17. SEM micrograph of 7.5% Sonicated NC mix for four different spots (a–d).

C-S-H with at least void-less core inside (in state of non-reacted NC
particles due to agglomerations), while it will result in continuous
solid core of high stiffness C-S-H (in state of well dispersed fully
reacted NC particles).
From the sonicated NC (7.5% Sonicated) micrographs, and in
addition to the dense, well compacted matrix, and the spread
presence of the CSH component within the matrix, a very signif-
icant action of the NC particles was recognized, where the NC
sheet-like acted as bridge connecting both sides of the crack
together and preventing the propagation of the crack in a perfor-
mance close to the action of fibers when arresting the cracks
(Fig. 17b–d).

Fig. 18. XRD of 7.5% as-received NC, 7.5% Sonicated NC, and the control concrete mixes.
254 N. Hamed et al. / Construction and Building Materials 205 (2019) 245–256

3.8. X-ray Diffraction (XRD)
XRD was performed to detect changes in the hydration products
due to the presence of NC before and after being exposed to ultra-
sonication, and relative to hydration products of a control sample
without the presence of NC particles.
Fig. 18 presented the XRD peaks of the control (C), 7.5% as-
received NC, and 7.5% sonicated NC mixes, due to its crystalline
nature, calcium hydroxide and calcium carbonate peaks appear
clearly in the XRD diagrams, while amorphous materials such as
calcium silicate hydrate cannot be directly detected by this tech-
nique [60]. The calcium hydroxide peaks could be clearly found
in Co mix, while by using the NC as a cement replacement, the
CH peaks decreased significantly for the mixes containing NC par-
ticles either; the as received or the sonicated. The decrease of the
CH peaks directly indicates the reactivity of NC particles, and indi-
rectly indicates higher C-S-H content in the mixes with NC substi-
tution as a result of the reaction of the silica and aluminosilicate
components in the NC with the excess calcium hydroxide (CH)
from cement hydration to produce extra Calcium-Silicate-
Hydrate (C-S-H) gel which enhances the ITZ among aggregates
and cement pastes and enhances the concrete strength [60]. The
7.5% mix with sonicated NC, showed much lower peaks of the CH
than the one with as-received NC particles. The calcite (CC) peaks
followed the trend of the calcium hydroxide peaks, which also
indicates much lesser content of CH in the mixes containing NC rel-
ative to the Co mix. The presence of the CH in large amounts ease
the reaction with the CO2 in the air producing more calcite (CaCO3)
as a result of the carbonation process, see Eq. (1).
this case, AFM images can be helpful for providing insight into the
interpretation of the mechanical properties of NC cement matrix.
As shown in Figs. 19–21, the AFM topography images of pol-
ished cement paste incorporating NC that indicate rounded parti-
cles grouped into clumps representing the CSH aggregated
particles, which supports the colloidal spheres model of C–S–H,
since the spherical features observed in Figs. 20 and 21 are of sim-
ilar size to the particles of the previously recognized shapes in the
literature [61]. Furthermore, the clumps appear to have relatively
small voids.
Taylor et al. [62] reminded us of Everett’s definition of gels as
‘‘dispersions in which the attractive interactions between the ele-
ments of the disperse phase are so strong that the whole system
develops a rigid network structure and, under small stresses,
behaves elastically”. C-S-H in hydrated tricalcium silicate paste
exactly fits this definition. AFM imaging of the flat surface of
hydrating cement paste [18,63], shows that the elements of the
disperse phase occur in the forming of identical aggregated
nanoparticles of C-S-H.

Ca(OH)2 + CO2 ! CaCO3 + H2 O ð1Þ

As final, the mixes could be arranged in reference to the CH and
CC contents as follows: 1-Co mix, 2-NC 7.5, and finally with the
lowest content the Sonicated 7.5% mix.

3.9. Atomic force microscope (AFM)

Figs. 19–21 show the topographical images from AFM of the

control cement matrix (without NC), 7.5% as-received NC matrix
(7.5% as-received NC), and 7.5% sonicated NC cement matrix
(7.5% Sonicated NC). Although the AFM images do not have a great Fig. 20. The AFM topographical of 7.5% as-received NC cement paste.
quantitative value other than for determination of morphology, in

Fig. 19. The AFM topographical of the control paste. Fig. 21. The AFM topographical of 7.5% Sonicated NC cement paste.
 N. Hamed et al. / Construction and Building Materials 205 (2019) 245–256
Images of C–S–H in hardened cement paste show nearly spher-
ical particles of different sizes in different areas. Typical sizes of
these spherical particles range reached to 465 nm for the as-
received NC cement matrix, while the range reached 721 nm for
the Sonicated NC cement matrix. AFM images of C–S–H gel with
brighter regions being higher than darker ones. The maximum
height difference between two different points in the image of
the 7.5% as-received NC matrix is 465 nm, as for the 7.5% Sonicated
NC the difference reached 721 nm.
When compared to Co mix, the presence of the CH plates could
be easily identified as with small clumps of the C-S-H particles, the
difference between the two phases is showing, rougher, bumpy
and grainy surface of the CSH compared to the smoother surface
of the CH region.
The surface topography as well as the particles morphology
with the wide spread of the CSH gels in the matrices containing
NC relative to the Co mix, and the complete absence of the CH
phases within the AFM images of 7.5% as-received NC, and 7.5%
Sonicated NC mixes highly indicate the reactivity of NC particles
that resulting in the previously observed tremendous mechanical
properties.
4. Conclusions
The following conclusions can be drawn from the test results;
1. The NC particles enhanced all studied mechanical properties of
concrete, especially when dispersed using the sonication.
2. The optimum percentage out of the studied cement substitu-
tions was 7.5% for both; the as-received NC, and the Sonicated
NC to enhance the studied mechanical properties of concrete.
3. The gains in the compressive, split tensile, flexural, and bond
strengths with Sonicated NC mixes were ranged from 1.42 to
3.74 times of the gains with those of as-received NC mixes.
4. For 12 mm rebars specimens, the slippage mode of failure was
the dominant behavior, while the split was dominant for
16 mm rebars specimens.
5. SEM showed the four major effect of the NC with the cement
matrix; (1) filling effect, (2) pozzolanic reactivity, (3) nucleation
effect, and (4) needle effect.
6. XRD and AFM results indicated the higher reactivity of Soni-
cated NC mixes as compared to the as-received NC mixes
resulting in a denser and well compacted matrix.
Conflict of interest
The authors declared that there is no conflict of interest.
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