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Effect of multi-walled carbon nanotubes (MWCNTs) on the strength

development of cementitious materials

Article  in  Journal of Materials Research and Technology · October 2018

DOI: 10.1016/j.jmrt.2018.09.006

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Original Article

Effect of multi-walled carbon nanotubes (MWCNTs)

on the strength development of cementitious
materials

Ali Naqi a,∗ , Naseem Abbas b,∗ , Nida Zahra c , Abasal Hussain d , Syed Qasim Shabbir e
a School of Civil & Environmental Engineering, Chung-Ang University, Seoul 06974, Republic of Korea
b School of Mechanical Engineering, Chung-Ang University, Seoul 06974, Republic of Korea
c Department of Physics, Government College University, Faisalabad 38000, Pakistan
d School of Civil Engineering, Dalian University of Technology, Dalian 116-024, China
e School of Civil & Environmental Engineering, Yonsei University, Seoul, Republic of Korea

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

Article history: The proposed study aimed to investigate the potential use of pristine multi-walled carbon
Received 11 April 2018 nanotubes (MWCNTs) as nano reinforcement in enhancing mechanical properties of hybrid
Accepted 5 September 2018 MWCNT/silica fume cement composites. Dispersion of MWCNTs was facilitated utilizing
Available online xxx very fine particles of silica fume which also helped in an improved interfacial bond between
MWCNTs and the cement matrix. The MWCNTs dispersion within the hardened cement
Keywords: matrix was qualitatively assessed by Field Emission Scanning Electron Microscope (FESEM)
Multi-walled carbon nanotubes analysis. It was also observed that addition of MWCNTs accelerated the hydration process.
Silica fume The test results showed an increment in compressive strength by 12.4% and reduction in
Dispersion of MWCNTs autogenous shrinkage by 8.5% for hybrid MWCNT/silica fume cement composites containing
Compressive strength 0.01% MWCNTs (by wt. of binder). However, higher additions (greater than 0.03%) of MWC-
Autogenous shrinkage NTs appeared to have adverse effects on specimens. It was found that properly dispersed
MWCNTs filled the fine pores in the cement matrix by providing an additional nucleation site
for the formation of calcium silicate hydrate (C-S-H) that results in a denser microstructure,
which in turn enhanced the strengths and limited the autogenous shrinkage.
© 2018 Brazilian Metallurgical, Materials and Mining Association. Published by Elsevier
Editora Ltda. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).

cement paste phase of concrete is apparently very brittle

1. Introduction
Concrete is the most widely used construction material for
buildings, bridges, roads and dams all over the world. It is the
second most used material (after water) on earth. However,
material and possesses very low tensile strength and low
strain capacity. Volume changes in concrete are generally
attributed to the drying of concrete but there is an additional
problem to drying shrinkage in early stages that occur without
any moisture transfer to the surrounding environment. This

∗
Corresponding authors.
E-mails: aliravian@cau.ac.kr (A. Naqi), naseem@cau.ac.kr (N. Abbas).
https://doi.org/10.1016/j.jmrt.2018.09.006
2238-7854/© 2018 Brazilian Metallurgical, Materials and Mining Association. Published by Elsevier Editora Ltda. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Please cite this article in press as: Naqi A, et al. Effect of multi-walled carbon nanotubes (MWCNTs) on the strength development of cementitious
materials. J Mater Res Technol. 2018. https://doi.org/10.1016/j.jmrt.2018.09.006
JMRTEC-492; No. of Pages 9
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volume decrease is termed as autogenous shrinkage and is
related to the chemistry and changes in the internal structure
[1,2]. Autogenous shrinkage should be controlled as it leads
to cracking [3]. The phenomenon of autogenous shrinkage
was identified a long time ago, but its practical importance
in concrete technology was highlighted in recent years. In
high-strength concrete, low water-binder ratio and inclusion
of natural admixture, e.g. silica fume, result in a substantial
drop in internal relative humidity value of the paste specimen
during sealed hydration [4]. This autogenous change in rela-
tive humidity is closely related to the autogenous shrinkage,
which results in internal tensile stresses due to restraint
from the aggregates. To control the aforementioned problem
researchers started testing macrofibres and microfibers as a
mean of reinforcement in cementitious composites at micro
level [5,6]. However, cementitious composites show flaws at
nanoscale where fiber reinforcement is not effective [7].
Carbon nanotubes (CNTs) are of particular interest because
of their high mechanical, electrical and thermal properties
and their ability to prevent cracks growth at the nanoscale
[8,9]. The nanotubes get their high stiffness and strength
from the carbon–carbon (C–C) covalent sp2 bonding between
individual carbon atoms. Carbon nanotubes are considered
as the strongest and stiffest nanomaterials discovered yet
in terms of elastic modulus and tensile strength, with a
reported Young’s modulus of nearly 1 tera-pascal (TPa), a
tensile strength of up to 100 giga-pascal and yield strain of
12% [10,11].
The two main challenges to encounter in order to achieve
an effective CNTs/cement composite are, well dispersed CNTs
within cement paste matrix and the bonding between nan-
otubes and the cement paste [12]. High aspect ratio and strong
surface attraction between CNT particles make it extremely
difficult to ensure uniform dispersion within the cement
paste [13]. Poor dispersion results in the formation of defect
sites in the cement paste matrix that leads to the forma-
tion of CNT bundles and limit the effectiveness of CNTs [14].
Researchers used a combination of physical (ultrasonication)
and chemical (use of surfactant) techniques to better disperse
CNTs in cement-based materials [15]. However, using a sur-
factant as a dispersant can cause issues of connectivity of
carbon nanomaterials within cement matrix [16]. A strong
bond between CNTs surfaces and cement paste is necessary
for crack bridging that can provide considerable mechanical
reinforcement [17]. Sanchez and Ince [18] utilize very fine par-
ticle sizes of silica fume, size ranging from 100 to 500 nm,
to overcome dispersion and bonding obstacles of nanofibers
within cement matrix. Silica fume particles can mechani-
cally separate the agglomerated MWCNTs within the cement
paste matrix allowing the elimination of ultra-sonication
process.
Cwirzen [19] used functionalized carbon nanotubes for the
reduction of autogenous shrinkage. His initial test results
showed an almost 50% decrease for 1.4 wt.% of CNTs. Exper-
imental results from Konsta-Gdotous et al. [20] showed a
decrease in autogenous shrinkage with an increase amount of
long MWCNTs compared to the reference plain cement paste.
Specimens reinforced with 0.048 wt.% of MWCNTs showed an
increase of 30–40% higher flexural strength over plain paste
specimen. Cwirzen et al. [21] achieved 50% higher compressive
Please cite this article in press as: Naqi A, et al. Effect of multi-walled carbon nanotubes (MWCNTs) on the strength development of cementitious
materials. J Mater Res Technol. 2018. https://doi.org/10.1016/j.jmrt.2018.09.006
strength for the cement paste specimen doped by MWCNTs
(0.045 wt.%), which were dispersed by sonication prior to mix-
ing in matrix. Collins et al. [22] demonstrated that with the
use of polycarboxylate admixture in combination with ultra-
sonication exerted positive influence on compressive strength
of cement paste. Shah et al. [20,23] have investigated the
effect of various dosages of CNTs, varying between 0.02 wt.%
and 0.1 wt.% by weight of cement, in cement paste speci-
mens and reported that low concentrations of CNTs leads
to more enhancement in mechanical properties of nanocom-
posites. Researchers have also studied the effects of CNTs
on frost durability [24] and sensing properties of pastes
and concretes. Li et al. [25] first developed piezo-resistive
MWCNTs/cement composites using functionalized CNTs and
measured the piezo-resistivity under uniaxial compression.
Saafi [26] developed the piezo-resistive SWCNT/cement sen-
sor for damage detection in concrete structures. Han et al. [27]
integrated self-sensing CNTs concrete into concrete pavement
and applied this payment to a real time detection of vehicles
passing.
The present study experimentally investigates the effects
of MWCNTs as nano reinforcement to enhance the com-
pressive strength and minimize the autogenous shrinkage of
MWCNTs/silica fume cement composites. The study involves
a real time internal relative humidity [IRH] sensor embed-
ded in fresh MWCNTs/silica fume cement composites and
connected to a CR1000 data logger to measure the fluctu-
ations in relative humidity values as autogenous shrinkage
is closely related to the relative humidity. Previous studies
did not undertake the relative humidity values for measur-
ing autogenous shrinkage in cement composites. Cement
composites with eight different amounts of MWCNTs addi-
tion: 0; 0.01; 0.02; 0.03; 0.05; 0.10; 0.20; and 0.30 wt.% of
binder were made. For each mixture the amount of silica
fume applied was fixed at 10% by weight of binder. The
role of silica fume in facilitating the dispersion of nanotubes
and improving the interfacial bond between the cement
phase and nanotubes is also studied. A polycarboxylate based
superplasticizer (SP) was applied to improve the flow of MWC-
NTs/cement composites and to enable proper dispersion of
nanotubes [18,28]. The MWCNTs dispersion within the hard-
ened cement matrix was qualitatively assessed by FESEM
analysis.
2. Experiment details
2.1. Materials
Type 1 Ordinary Portland cement (OPC) (Sungshin Cement Co.,
Ltd.) and silica fume (Gansu Sanyuan Silicon Materials Co.,
Ltd.) were used in this study. Table 1 shows chemical com-
position of OPC and silica fume. Pristine MWCNTs that are
a proprietary product of KUMHO Petro-chemicals were used
in the specimens. The MWCNTs were produced with purity
greater than 90% by weight. Table 2 shows the general speci-
fications of MWCNTs used in this work. The polycarboxylate
based superplasticizer was collected in liquid packing from
Sure Chemical Co., Ltd.). The specifications of superplasticizer
are listed in Table 3.
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Table 1 – Chemical composition of Portland cement and Table 4 – Mix design of test specimen. Unit [g].
silica fume. Pristine Water Admixture
Binder
Constituent OPC (mass %) Silica fume (mass %) MWCNTs (SP)
Cement Silica fume
SiO2 21.9 93.0
Al2 O3 4.9 0.4 900 100 0.00 200 0.50
Fe2 O3 3.7 0.5 900 100 0.10 200 0.70
CaO 62.3 0.7 900 100 0.20 200 1.10
MgO 2.0 0.5 900 100 0.30 200 1.50
K2 O 0.5 0.8 900 100 0.50 200 2.00
Na2 O 0.3 – 900 100 1.00 200 2.50
SO3 2.2 – 900 100 2.00 200 5.50
LOI 1.78 1.5 900 100 3.00 200 7.80
Sum 99.5 97.4
mixed for 5 min. Water was added followed by superplasti-
cizer after 2 min and mixed again for an additional 5 min at
Table 2 – Specifications of MWCNTs (K-Nanos 100P).
low speed. Mixing was finished with 5 min additional mixing
Property Unit Value at high speed.
CNT type – Bundle
Bundle diameter ␮m 3–15 2.3. Experimental procedure
Bundle length ␮m 10–50
Outer diameter nm 10–15
All the specimens were demolded after 24 h of casting and
Bundle density g/ml 0.02–0.04 cured in water saturated with calcium hydroxide till the time
Purity >90 0.45 of testing. The hardened specimens after 7-days curing were
Crystallinity IG/ID 0.6–0.8 crushed and pre-conditioned for the microstructure and frac-
ture surfaces analysis using FESEM-6330F, JEOL Ltd., Tokyo,
Japan. Moreover, energy dispersive spectroscopy (EDS) tech-
Table 3 – Specifications of polycarboxylate based
superplasticizer. nique was used to confirm the presence of MWCNTs and
distinguish them from needle-like products which have simi-
Property Specification
lar structure like MWCNTs, by verifying chemical composition.
Visual appearance Pale brown viscous liquid Cube specimen of 50 × 50 × 50 mm size were prepared with
Density (23 ◦ C) 1.12 ± 0.2 kg/l MWCNTs concentration of 0; 0.01; 0.02; 0.03; 0.05; 0.10; 0.20;
pH (23 ◦ C) 9.0 ± 0.5 and 0.30 wt.% of binder, cured at a constant temperature of
Solid content (%) 40 ± 0.5
23 ± 1 ◦ C and relative humidity of 100% according to the ASTM
Stability (0 ◦ C, 24 h) No crystallization
Cl– (%) ≤0.10
C 192. Compressive strength testing was done according to
Na2 SO4 (%)Na2 O + 0.658K2 O (%) ≤4.0 ≤5.0 ASTM C 109 at 1–3-7 day’s age. The internal relative humidity
(IRH) in specimens was continuously monitored using SHT75
temperature and humidity sensors. In order to use this sen-
2.2. Mixes preparation sor, a data logger is attached to collect data and uses CR1000
software manufactured by US company. Fig. 1a shows an
A total of eight mixes were prepared and examined. Eight dif- experimental view of the IRH measurement of the SHT75 tem-
ferent quantities of MWCNTs, 0; 0.01; 0.02; 0.03; 0.05; 0.10; 0.20; perature and humidity sensor and hybrid MWCNT/silica fume
and 0.30 wt.% of binder were added. The concentrations are cement composite prepared for use in this study. Fig. 1b shows
denoted by C0.00; C0.01; C0.02; C0.03; C0.05; C0.10; C0.20; and vicat needle test setup to check the setting time of the speci-
C0.30, respectively. Silica fume was added in an amount of mens. Fig. 1c shows specimens wrapped in aluminum foil after
10% by weight of binder (S10) in each mixture to evaluate its final set while Fig. 1d shows apparatus utilized to measure the
effect on MWCNT/cement composite. The amount of water length change of the specimen.
added to all the mixtures was kept constant at 20% by weight The autogenous shrinkage testing of hybrid MWCNT/silica
of binder. The idea of utilizing less water-binder ratio is to fume cement composites was done in accordance with ASTM
enhance CNTs dispersion by very fine particles of silica fume. C 490. The paste was cast into a 25 × 25 × 254 mm prism. The
When the water quantity in the cement matrix is reduced, setting time of paste was determined by using vicat apparatus
the possibility of collision between the agglomerated MWC- according to ASTM C 191. Immediately after final set, spec-
NTs and silica fume particles is increased [28–30]. Another imens were demolded and wrapped using aluminum foil. A
reason of avoiding high water-binder ratio is the formation of length comparator was used to measure the distance between
agglomerates as black streaks of nanotubes within the cement the studs from the final setting time up to 6 days.
paste samples following mixing [31]. The amount of super-
plasticizer (SP) varied between 0.05 and 0.8 wt% of the binder.
3. Results and discussion
Table 4 shows mix design of test specimen. In order to prepare
hybrid MWCNT/cement composites, mixing of material was 3.1. Compressive strength
carried out using standard Hobart mixer, specified in Ameri-
can Society for Testing Materials (ASTM) C 305. All the dried The addition of pristine multi-walled carbon nanotubes has
materials including cement, silica fume and MWCNTs were affected the compressive strengths of cement/silica fume

Please cite this article in press as: Naqi A, et al. Effect of multi-walled carbon nanotubes (MWCNTs) on the strength development of cementitious
materials. J Mater Res Technol. 2018. https://doi.org/10.1016/j.jmrt.2018.09.006
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a b

c d

Fig. 1 – (a) RH sensors embedded in the specimen. (b) Measurement of final setting time of paste using vicat needle. (c)
Specimens wrapped in aluminum foil after final set. (d) Apparatus used to measure length change of prism specimen.

paste specimens. The values were measured after 7 days of 80

S10-C0.00 S10-C0.01
water curing. Fig. 2 shows compressive strengths of hybrid
75 S10-C0.02 S10-C0.03
MWCNT/silica fume cement composites reinforced with vary- S10-C0.05 S10-C0.10
ing amounts of MWCNTs (by wt. of binder) at different ages.
Compressive Strength (MPa)

S10-C0.20 S10-C0.30
70
The maximum compressive strength was achieved in sam-
ples with 0.01% MWCNTs. The specimens had 4.4%, 9.7%, and 65

12.4% higher compressive strengths than that of reference

60
specimens at 1, 3 and 7 days respectively. Also, other speci-
mens with low dosages showed higher compressive strengths 55
as compared to the reference specimens. The 1, 3, and 7-
day compressive strengths of specimens with 0.02% MWCNTs 50

were about 0.2%, 7.9%, and 6.8% greater, while specimens with
45
0.03% MWCNTs produced 5.2%, 3%, and 4.1% higher compres-
sive strength than that of reference specimens, respectively. 40
1 2 3 4 5 6 7
Morsy et al. [32] showed similar results by improving com-
Age (Days)
pressive strength by 11% on addition of CNT (0.02 wt.%) and
nano metakaolin (6 wt.%) while Cwirzen et al. [21] improved Fig. 2 – Compressive strength of hybrid MWCNT/silica fume
compressive strength by 50% for specimen with an addition cement composites reinforced with varying amounts of
of 0.045% MWCNTs compared to reference samples. MWCNTs at different ages.
An amount of maximum of 1% nanotubes (by weight of
total cement) addition to the mixes enhanced the compressive

Please cite this article in press as: Naqi A, et al. Effect of multi-walled carbon nanotubes (MWCNTs) on the strength development of cementitious
materials. J Mater Res Technol. 2018. https://doi.org/10.1016/j.jmrt.2018.09.006
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a b

MWCNTs bridging
the hydrates MWCNTs bridge
the nano crack

— 100 nm
— 100 nm x162000 x150000

Fig. 3 – SEM image of (a) MWCNTs bridging hydrates, (b) evidence showing MWCNTs bridging a nano-crack.

a b

MWCNTs embeded
ih hydrated matrix

MWCNTs
embeded in
paste

−100 nm x50000
1 Um x25000

c d
MWCNTs covered with
hydration product
MWCNTs entangled
in clumped silica
fume

−100 nm
—100 nm x159000 x75000

Fig. 4 – SEM image of (a, b) individually dispersed MWCNTs fibers embedded in hydration product (c) MWCNTs covered
with hydration product (d) MWCNTs entangled in clumped silica fume(d).

strength of the cement composites [7,33]. The plausible reason
for this effect is that the smaller concentrations of MWCNTs
agglomerates were easier to be dispersed by the silica fume
into individual fibers that might act as pores and filled the pore
space between the cement grains with hydration phases and
reduced the capillary porosity [34,35]. The reduction in poros-
ity leads to a denser microstructure than that of reference mix.
Work by Nochaiya [36] showed that MWCNTs additions results
in fewer mesopores than that of control mix. Due to their very
small size, MWCNTs provide very large reactive surface areas
that can provide additional nucleation site. The interfacial
bond between the hydration product and MWCNTs depends
on the surface energies of MWCNTs and hydrated product,
while surface energies of CNTs ranged from 27 to 45 mj/m2 [37].
The interface between MWCNTs and the hydrated matrix is
improved by bridge effect and well dispersed MWCNTs would
act as reinforcement fibers [22]. Fig. 3a and b shows carbon
nanotubes bridging hydrates and nano-cracks respectively.
Fig. 4a and b shows individually dispersed fibers embed-
ded in the hydrated matrix. The FESEM images confirmed
that these individually dispersed MWCNTs fibers could act
as additional nucleation sites for the calcium silicate hydrate
formation. Fig. 4c shows MWCNTs covered with hydration
products. Makar and Chan [38] also obtained same images
where single-walled carbon nanotubes (SWCNTs) were cov-
ered with C–S–H layer. Fig. 4d shows MWCNTs entangled in
clumped silica fume. Chaipanich et al. [39] and Torkittikul et al.
[40] showed an increase in compressive strength by 10% for
specimens reinforced with 1% CNTs by weight of cement at
7 days testing age. While the test results of Musso et al. [41]
showed an increase of 11% in compressive strength utilizing
0.5% pristine CNTs by weight of cement. However, all these test
results include sonication method to disperse CNTs prior to
mixing with other aggregates. On the other hand, in this study,

Please cite this article in press as: Naqi A, et al. Effect of multi-walled carbon nanotubes (MWCNTs) on the strength development of cementitious
materials. J Mater Res Technol. 2018. https://doi.org/10.1016/j.jmrt.2018.09.006
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additions of MWCNTs, 0.05; 0.10; 0.20; and 0.30 wt.% obtained 0

lower compressive strengths as compared to the reference -200
S10-C0.00 S10-C0.01

Autogenous Shrinkage (10-6mm/mm)

S10-C0.02 S10-C0.03
specimens. The compressive strengths of specimens with
-400 S10-C0.05 S10-C0.10
0.05 wt.% MWCNTs were 0.1, 3.2 and 1.0% lower. Specimens S10-C0.20 S10-C0.30
-600
with 0.10 wt.% MWCNTs showed 0.7, 4.2 and 4.1% lower com-
pressive strengths, while specimens with 0.20 and 0.30 wt.% -800
MWCNTs showed 10.4, 12.9, 12.4, 17.7, 21 and 20% less com- -1000
pressive strengths compared to the reference specimen at 1, 3
-1200
and 7 days respectively. Similar results are revealed by Morsy
-1400
et al. [32] that compressive strength increased at low dosage of
MWCNTs until it reaches an optimal amount of 0.02 wt.% and -1600
then values started to drop. Kowald [42] incorporated MWC- -1800
NTs in range of 0.5 and 5 wt.% into the cement paste and
-2000
found that low concentrations have enhanced the compres- 0 1 2 3 4 5 6
sive strength while higher dosages have reduced the strength Time after demolding (Days)
values compared to the reference specimen. This decrease
Fig. 6 – Autogenous shrinkage of hybrid MWCNT/silica
in compressive strength for the higher amount of MWCNTs
fume cement composites reinforced with varying dosages
can be related to the inadequate dispersion as well as pres-
of MWCNTs as a function of time.
ence of agglomerates and bundles of MWCNTs around cement
grains hindering the formation of hydration product resulting
in weak bond. Also, nanotubes may not be wetted adequately -2000
thus causing pullout resulting in the formation of cracks [43].
Autogenous Shrinkage (10-6mm/mm) -1900 3-days (Age)

3.2. Internal relative humidity (IRH) -1800

-1700
Fig. 5 shows internal relative humidity values of all speci-
-1600
mens with varying amounts of MWCNTs. Specimen with the
dosage of 0.01 wt.% MWCNTs showed least drop in relative -1500
humidity among all other specimens that is approximately
-1400
5.5% less drop in IRH as compared to the reference specimen
(silica fume composites). Specimen with 0.02 wt.% MWCNTs -1300

dosage showed 2.5% less drop in IRH compared to reference -1200

specimen while specimen with 0.03 wt.% dosage of MWCNTs
-1100
showed nearly equal drop in IRH compare to the reference 0.00 0.05 0.10 0.15 0.20 0.25 0.30
one. Fewer drops in relative humidity compared to the refer- % MWCNTs (By Weight of binder)
ence specimen indicate that smaller additions results in lower
hydration rate of cement. In the case of low dosages, the indi- Fig. 7 – Autogenous shrinkage of specimens with varying
vidually dispersed MWCNTs had decreased the number of fine dosages of MWCNTs at 3-days age.
pores in the specimen, which results in a reduction of capillary
stresses and ultimately lower autogenous shrinkage. However,
specimens with 0.05; 0.10; 0.20; and 0.30 wt.% MWCNTs pro-
100 duced quick drops of internal relative humidity with 8.5 and
8% more drop in IRH than that of the reference specimen. The
98
reason for these higher drops in relative humidity can possibly
96
be the smaller internal pore structure in the paste and inabil-
Internal Relative Humidity (%)

94 ity of MWCNTs to fill the fine pores due to agglomerates and

92
bundles of MWCNTs. Indeed, according to the Kelvin equation,
small pore sizes gives reduce radii of water meniscus result-
90
ing in quick decrease of the internal relative humidity, which
88 ultimately induce stress and enlarge shrinkage.
86
S10-C0.00 S10-C0.01 3.3. Autogenous shrinkage
84
S10-C0.02 S10-C0.03
82 S10-C0.05 S10-C0.10
Fig. 6 shows the measured autogenous shrinkage as a func-
S10-C0.20 S10-C0.30
80 tion of time for varying dosages of MWCNTs. Figs. 7 and 8
0 1 2 3 4 5 6
exhibit a graphical presentation of shrinkage values at 3 and 6
Age (Day)
days’ age. The shrinkage values were zeroed at the final setting
Fig. 5 – Internal relative humidity of hybrid MWCNT/silica time, which varies with varying amounts of MWCNTs incorpo-
fume cement composites reinforced with varying amounts rated in the specimen. According to the measured autogenous
of MWCNTs. shrinkage values, specimen with an addition of 0.01 wt.%

Please cite this article in press as: Naqi A, et al. Effect of multi-walled carbon nanotubes (MWCNTs) on the strength development of cementitious
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JMRTEC-492; No. of Pages 9
-2000
-1900
Autogenous Shrinkage (10-6mm/mm)
-1800
-1700
-1600
-1500
-1400
-1300
-1200
-1100
0.00 0.05 0.10
% MWCNTs (By Weight of binder)
Fig. 8 – Autogenous shrinkage of specimens with varying
dosages of MWCNTs at 6-days age.
Table 5 – Influence of MWCNTs on cement paste final
setting time.
Specimen ID
S10-C0.00
S10-C0.01
S10-C0.02
S10-C0.03
S10-C0.05
S10-C0.10
S10-C0.20
S10-C0.30
MWCNTs showed highest reduction to 1413.385 ␮mm/mm fol-
lowed by specimen with 1503.937 ␮mm/mm reduction for an
addition of 0.02 wt.% MWCNTs in comparison to the refer-
ence specimen that showed reduction to 1543.307 ␮mm/mm
at 6 days age. These measured values are in accordance
with the findings of Blandine et al. [44]. Their experiment
showed highest autogenous reduction at an additional level
of 0.01 wt% which is 50% less shrinkage value than the ref-
erence paste specimen. Experimental results of Metaxa et al.
[45] also showed decreased autogenous shrinkage values for
the cement paste reinforced with 0.048 wt.% MWCNTs com-
pared to the plain cement paste. The influence of MWCNTs
to the autogenous shrinkage is related to the hydration of
cement. Vicat needle test was utilized to analyze the effect
of MWCNTs on the cement hydration. It was observed that
MWCNTs have an accelerating effect on hydration of cement
as varying dosages of MWCNTs showed differing final set-
ting time. Table 5 shows final setting time of specimens
with and without an addition of MWCNTs. It is evident from
the table that the final setting time of hybrid MWCNT/silica
fume cement composites was always less than the reference
specimen that confirms shortening of setting time of hybrid
MWCNT/silica fume cement composites by incorporation of
MWCNTs. These results endorse the findings of Maker and
Margeson who found a similar trend of final setting time
for CNTs [46]. Fig. 9 shows the position of peak energy dis-
persive (keV) from spectrum. Table 6 describes atomic % of
different elements in elemental analysis of energy dispersive
Please cite this article in press as: Naqi A, et al. Effect of multi-walled carbon nanotubes (MWCNTs) on the strength development of cementitious
materials. J Mater Res Technol. 2018. https://doi.org/10.1016/j.jmrt.2018.09.006
ARTICLE IN PRESS
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Spectrum 4
6-days (Age)
0 2 4 6 8 10 12 14 16 18
Full scale 4873 cts cursor: 0.000 keV
0.15 0.20 0.25 0.30
Fig. 9 – EDS analysis of 0.3 wt.% hybrid MWCNTs/silica
fume paste.
spectroscopy that confirms the presence of dispersed multi-
walled carbon nanotubes in the mixture. Owing to their very
small size the well-dispersed MWCNTs (diameter 8–15 nm)
can fill the fine pores between the cement grains and their
very large reactive surface areas can act as an additional nucle-
Setting time(h:min) ation site for the formation of calcium silicate hydrate (C-S-H).
5:55 This leads to reduced capillary stresses that result in lower
5:45 shrinkage. The mechanism for MWCNTs effect on cement
5:45 hydration resembles to Jeffrey J. Thomas model that shows
5:35 impact of well-dispersed nanoparticles on cement hydration
5:25
[34]. Fig. 10 shows hydration of cement [A] and with nanoparti-
5:15
cle [B] at different times after mixing. FESEM images confirmed
5:00
4:40 the presence of individually dispersed MWCNTs fibers within
the hydration product that possibly provided additional nucle-
ation site for C-S-H formation. However, higher additions
of MWCNTs 0.03; 0.05; 0.10; 0.20; and 0.30 wt.% were not
found to be effective in autogenous shrinkage reduction of the
hybrid MWCNT/silica fume cement composites as these addi-
tions showed increment in measured shrinkage compared to
the reference specimen. Although, these results contradict
with the findings of Cwirzen [19] and Konsta-Gdotous et al.
[20] which showed a decrease in autogenous shrinkage with
an even higher percentage of MWCNTs (1.4 and 0.048 wt.%
long MWCNTs respectively) compared to the reference plain
cement paste. The reason for increased autogenous shrinkage
in this study is related to the quick drops in internal relative
humidity, possibly due to the smaller internal pore structure in
the cement paste and inability of MWCNTs to fill the fine pores
due to agglomerates and bundles of MWCNTs. In fact, accord-
ing to the Kelvin equation, small pore sizes gives reduce radii
of water meniscus resulting in quick decrease of the internal
relative humidity, which ultimately induce stress and enlarge
shrinkage.
4. Summary and conclusion
In this study, mechanical properties of hybrid MWCNT/silica
fume cement composites have been investigated at concen-
trations of 0.01; 0.02; 0.03; 0.05; 0.10; 0.20 and 0.30% pristine
multi-walled carbon nanotubes (by weight of binder). The
specimens were made with 0.20% water-binder ratio and
tested through the compressive strength test and autogenous
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composites due to the formation of smaller internal pore

Table 6 – Elemental analysis of energy dispersive
spectroscopy. structure within the paste and inability of the entangled
and clumped MWCNTs to fill the fine pores.
Element Weight (%) Atomic (%)

C 4.75 8.55
O 48.99 66.19 Conflicts of interest
Mg 0.44 0.39
Al 0.34 0.27
The authors declare no conflicts of interest.
Si 1.09 0.84
S 0.19 0.13
Ca 42.87 23.12
Fe 1.33 0.51 Acknowledgements

This research was supported by Chung Ang University under

A B
1 Cement grain
Chung-Ang University Young Scientist Scholarship (CAYSS)
program. Furthermore, the support from Korean Conformity
Laboratories staff in testing of specimens is greatly appreci-
ated.
Nanoparticles

references

2
Hydration product
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Fig. 10 – Hydration of cement (A) and with nanoparticle (B)
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i) Silica fume particles were found to be effective to mechan-
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ii) Individually dispersed MWCNTs filled the fine pores
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iv) FESEM images confirmed the multi-wall carbon nanotubes
bridging hydrates and nano-cracks respectively.
v) Higher dosages (greater than 0.03 wt.%) of MWCNTs
appeared to have adverse effects on MWCNT/cement
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