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Materials Today: Proceedings 4 (2017) 6065–6071 www.materialstoday.com/proceedings

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The effect of carbon nanotubes and silica fume on compressive

strength and flexural strength of cement mortars
Arnon Chaipanicha,*, Rattiyakorn Rianyoia, Thanongsak Nochaiyaa,b
a
Department of Physics and Materials Science, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand.
b
Department of Physics, Faculty of Science, Naresuan University, Phitsanulok 65000, Thailand. (present affiliation, formerly at affiliation a
during the author’s Ph.D study.)

Abstract

This paper reports the effect of carbon nanotubes on compressive strength and flexural strength of Portland cement- silica fume-
carbon nanotubes cement mortars. Silica fume, by-product from silicon metal and ferro-silicon alloys industries was used as a
cement replacement material at 10 % by weight. Carbon nanotubes, produced by CVD method was used as an additional material
up to 1 % by weight. Water to binder ratio (w/b) of 0.5 was used for all mortar mixes. Samples were cured in water until being
tested at the age of 28 days. The results show that the mortar with silica fume has higher compressive strength and flexural
strength than Portland cement control and when used in combination with carbon nanotubes a further increase in compressive
strength and flexural strength were observed with the optimum strengths obtained at 0.5% CNTs.

© 2017 Elsevier Ltd. All rights reserved.

Selection and Peer-review under responsibility of International Conference on Science and Technology of the Emerging
Materials.

Keywords:Carbon nanotubes; Composites; Silica fume; Compressive strength; Flexural strength

* Corresponding author. Fax: +66-53-943445.

E-mail address:arnon.chaipanich@cmu.ac.th; arnonchaipanich@gmail.com

2214-7853© 2017 Elsevier Ltd. All rights reserved.

Selection and Peer-review under responsibility of International Conference on Science and Technology of the Emerging Materials.
6066 Arnon Chaipanich et al. / Materials Today: Proceedings 4 (2017) 6065–6071

1. Introduction

Portland cement of ASTM type I (PC) produced by The Siam Cement Public Company Ltd., Lampang, Thailand
was used as a control mix. Silica fume (SF), a by-product of the ferrosilicon industry is a very fine pozzolanic
material consists of very small spherical particles of amorphous silica (≈100 nm). SF is usually used to give high
strength in concrete due to its improvement to the concrete mechanical properties. The optimum usage of SF is
reported to be in the range of 7.5-10% as Portland cement replacement [1-3] and often is investigated at 10% [4].
CNTs are carbon material with a cylindrical nanostructure having same characteristic as tubes of graphite sheet
withnano-size diameter which have excellent mechanical properties (tensile strength as high as 200 GPa) [5, 6]
Interests in the cement and concrete industries have resulted in increasing recent research in using CNTs as an
additive in cements [7-9]. The improvements in terms of compressive strength when using CNTs (up to 1%) in
Portland cement [10, 11] and in Portland-fly ash cement [7] were reported due to its physical densification of the
matrix [7, 12]. In this study, silica fume which is a sub-micron material were used in combination with CNTs a
nano-sized material where both materials has the prospect to be used in small amount to enhance the mechanical
properties by densification of cement matrix. The effects of SF with CNTs on the compressive strength and flexural
strength of cement mortars are investigated.

2. Materials and Methods

2.1. Material and sample preparation

Portland cement of ASTM type I (PC) produced by The Siam Cement Public Company Ltd., Lampang, Thailand
was used as a control mix (scanning electron microscope of PC shown in Fig. 1a). Silica fume (SF) obtained from
Elkem Silicon Materials Ltd., Singapore was used to replace Portland cement at 10 wt%. It is spherical shape with
the particle size approximately 50 nm to 1 μm (Fig. 1b).
Multi-walled carbon nanotubes (CNTs), used as an additive material up to 1 wt% of cement was synthesized by
an infusion chemical vapour deposition (CVD) method using nickel oxide as a catalyst. CNTs dimensions are∼50
nm in diameter and ≥500 nm in length (Fig. 1c).
X-ray diffraction (XRD) patterns of raw materials are shown in Fig. 2. XRD trace of Portland cement (Fig. 2a)
indicates compounds of Portland cement showing clear peaks of C3S and C2S. XRD trace of silica fume shows
board peak corresponds to amorphous phases as shown in Fig. 2b. The dominant peaks of CNTs (Fig. 2c) are carbon
that matches JCPDF file No.751621 and a minor peak of nickel which occurred during synthesis.
 Arnon Chaipanich et al. / Materials Today: Proceedings 4 (2017) 6065–6071 6067

Fig. 1. SEM micrograph of (a) Portland cement; (b) silica fume; (c) carbon nanotubes.

Fig. 2. XRD pattern of (a) Portland cement; (b) silica fume; (c) carbon nanotubes.
6068 Arnon Chaipanich et al. / Materials Today: Proceedings 4 (2017) 6065–6071

Mix proportions of the cement mortars with and without silica fume as a cement replacement (at 10% by weight
of PC) and CNTs are given in Table 1. A rotary mixer was used for mixing. CNTs were dispersed in water
(calculated from w/b of 0.5) using ultrasonic bath (Elma: Elmasonic E 30H) for 30 min. For homogeneous mixing,
the binders (PC and SF) were first blended in the mixer for 3 min before mixing with water, using water to binder
(w/b) ratio of 0.5. River sand, sand to cement ratio of 2.5, was added and then mixed for another 2 min. After that,
the mixes were poured into oiled molds (50×50×50 mm3 and 40×40×160 mm3 for compressive strength and flexural
strength, respectively), compacted, surfaced-smooth and covered with plastic film for 24 h. The specimens were
then removed from the molds and cured in saturated lime water at a constant room temperature until test.

Table 1. Mix proportions of paste and mortar mixes.

Proportion (%)
Mix
PC SF CNTs Water Sand
PC 100 0 0 50 250
10SF 90 10 0 50 250
10SF0.5CNTs 90 10 0.5 50 250
10SF1CNTs 90 10 1 50 250

2.2. Compressive strength test

Three cube specimens (50×50×50 mm3) of each mix were prepared for compressive strength testing (Technotest:
MODENA, Italy) at 28 days according to ASTM C109at the rate of 1,250 N/s. The compressive strength values can
be calculated from Eq. 1.

= (1)

Where:
fm = Compressive strength (MPa).
P = Total maximum load (N).
A = Area of loaded surface (mm2).

2.3. Flexural strength test

Three bar samples (40×40×160 mm3) of each mix after curing at 28 days were carried out for flexural strength
test, according to ASTM C348, using the universal testing machine (HOUNSFIELD series H10KS) and then
calculated from Eq. 2.

= (2)

Where : σf = Flexural strength (MPa).

P = Load at a given point on the load deflection curve (N)
L = Support span (mm).
b = Width of test beam (mm).
d = Depth of tested beam (mm).
 Arnon Chaipanich et al. / Materials Today: Proceedings 4 (2017) 6065–6071 6069

3. Results and Discussion

3.1. Compressive strength

The effect of silica fume (10%) and carbon nanotubes (0.5% and 1%) on the compressive strength of cement
mortars is shown in Fig. 3. It can be seen that the 28 days compressive strength of Portland cement mortars with 10
% SF is noticeably higher than that of control mix (PC) where the relative compressive strength to PC is calculated
to be ≈110%. This is due to the fast pozzolanic reaction of SF together to give calcium silicate hydrates and the filler
effect of SF [13-15].Moreover, when carbon nanotubes is added at 0.5 % (10SF0.5CNTs), the compressive strength
increased to 69 MPa with relative strength to PC at ≈117%. The compressive strength of mortar with 1% CNTs
(10SF1CNTs) is found at 67.5 MPa which is slightly lower than the 0.5% CNTS mix but remain higher than the
10% SF mix without CNTs and the control PC mix. The improvement when using CNTs with SF is likely due to the
physical contribution of CNTs which further fill the matrix in combination with SF. At 0.5% by weight appear to be
optimum and at 1.0% CNTs a slight drop in compressive strength was found due to increase agglomeration of
CNTs. The filling effect of CNTs is reported by several researchers [7, 10-11].

Fig. 3. Compressive strength of Portland cement-silica fume-CNTs mortars at 28 days.

3.2. Flexural strength

The flexural strength of mortars with SF and in combination with CNTs at 28 days is shown in Fig. 4.A slight
increase in flexural strength can be seen with SF mix when compared to that of PC control mix. Moreover, the
highest flexural strength was found for10SF0.5CNTs and 10SF1CNTs mixes where the increase in flexural strength
can be clearly seen (Relative flexural strengths to PC for both mixes are found to be ≈110%). The increase in the
flexural strength is thought to be not only from CNTs filling the pores of hydration [7, 11] but also from the tubes
bridging effect providing reinforcement to the matrix which contribute to better resistance to flexure [11].Although
it must be noted that the benefits will largely depend on the dispersion where individual strands separately dispersed
would give better contribution than the agglomerated CNTs.
6070 Arnon Chaipanich et al. / Materials Today: Proceedings 4 (2017) 6065–6071

Fig. 4. Flexural strength of Portland cement-silica fume-CNTs mortars at 28 days.

The improvement on the flexural strength, when incorporated CNTs with silica fume can be seen to be similarly
to when using pristine CNTs in Portland cement-based system [10]. However, the relative improvement compared
to the mix without CNTs in flexural strength is slightly lower than those found in compressive strength in this
investigation. This perhaps can be explained by the possible agglomeration of CNTs that may occurred in the
systems, thus giving a filling effect thereby densifying the matrix more so than giving bridging strands of CNTs
required for flexural strength. Therefore, the effect of CNTs on the flexural strength would depend greatly on the
dispersion of CNTs more so than in compressive strength.

3.3 Microstructure

Microstructure of Portland cement-silica fume-carbon nanotubes composite using a scanning electron microscope
(SEM) is shown in Fig. 5. SEM micrograph showed calcium silicate hydrate (C-S-H), fibrous phase, which occurred
from Portland cement hydration reaction and from pozzolanic reaction between silica fume and calcium hydroxide.
Moreover, carbon nanotubes (as marked by the arrow) and SF (some remaining SF seen as spherical shape) can be
seen to densify the cement matrix by the filling effect.

Fig. 5.SEM micrograph of Portland cement-silica fume-CNTs paste at x 15,000.

 Arnon Chaipanich et al. / Materials Today: Proceedings 4 (2017) 6065–6071 6071

4. Conclusions

The use of SF resulted in the improvement of both compressive and flexural strength due to the filler effect and
pozzolanic reaction of SF. When incorporating CNTs with SF, the physical contribution of CNTs resulted to a
further increase in compressive strength and flexural strength. The optimum is seen at 0.5% CNTs for compressive
strength due to the physical filling effect, the possible agglomeration of CNTs at higher percentage would result to
reduction in compressive strength although a higher strength is still found compared to the mixes without CNTs.
The improvement on the flexural strength, when incorporated CNTs with silica fume, can be seen up to 1% where
flexural strength of mixes with 0.5% and 1% CNTs were found to be higher than both PC control and SF mixes
without CNTs. It must be noted that the effect of CNTs with SF on compressive strength and flexural strength would
thus largely depend on the dispersion of CNTs.

Acknowledgements

The authors would like to thank the Thailand Research Fund (TRF), Faculty of Science and Chiang Mai
University for the research grant given to Associate Professor Dr. Arnon Chaipanich. The authors would also like to
thank the Office of the Higher Education Commission, Thailand for supporting the grant fund given to Dr.
Thanongsak Nochaiya under the program Strategic Scholarships for Frontier Research Network for the Join Ph.D.
Program Thai Doctoral degree.

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