Chapter 30

MWCNT and CNF Cementitious Nanocomposites

for Enhanced Strength and Toughness

P.A. Danoglidis, M.G. Falara, M.K. Katotriotou, M.S. Konsta-Gdoutos, and E.E. Gdoutos

Abstract Cementitious nanocomposites reinforced with carbon fibers at the nanoscale were fabricated and tested,
exhibiting remarkably improved mechanical and fracture properties. The cementitious nanocomposites were reinforced
with well dispersed multiwall carbon nanotubes (MWCNTs) and carbon nanofibers (CNFs). A dispersion method involving
the application of ultrasonic energy and the use of a superplasticizer was employed to prepare the nanoscale fiber
suspensions. Flexural strength and Young’s modulus were experimentally investigated and compared with similarly
processed reference cement based mixes without the nano-reinforcement. The nanocomposites’ fracture properties were
also determined using the two parameter fracture model (TPFM). The excellent reinforcing capability of MWCNTs and
CNFs is demonstrated by a significant improvement in flexural strength (87 % for MWCNTs and 106 % for CNFs
reinforcement), Young’s modulus (100 %), and fracture toughness (86 % for MWCNTs and 119 % for CNFs reinforcement).

Keywords Multi-walled carbon nanotubes • Carbon nanofibers • Mortars • Fracture mechanics • Young’s modulus

30.1 Introduction

Cementitious materials suffer from low tensile strength and limited strain capacity, which gives rise to the formation of
nanocracks under relatively low tensile loads. The use of new reinforcing materials like multiwall carbon nanotubes
(MWCNTs) and carbon nanofibers (CNFs) makes it possible to produce cement based nanocomposites with revolutionary
properties. These materials, with aspect ratios greater than 1000, have Young’s modulus around 1 TPa [1] tensile strength of
65–93 GPa, and maximum strain of 10–15 %. However MWCNTs form agglomerates or bundles and adhere together with
van der Waals forces, which make it particularly difficult to separate. Early attempts to add MWCNTs to cementitious
materials have failed due to poor adhesion. Konsta-Gdoutos and coworkers [2, 3] developed a revolutionary method for
effective dispersion of MWCNTs in cement pastes, mortars and concrete. The dispersion of different lengths of MWCNTs
and CNFs in water was achieved by applying ultrasonic energy and using a surfactant. Recent and ongoing research by the
same authors have focused on developing multifunctional cement paste nanocomposites with high strength and advanced
strain detection ability that can be used as a novel self-sensing nanoreinforced cementitious structural material. The
incorporation of highly dispersed MWCNTs and/or CNFs at low concentrations has been shown to effectively arrest the
cracks at the nanoscale, imposing significant improvements in the mechanical properties of the nanocomposites [4–8]. While
a few studies on the mechanical strength of cementitious systems containing MWCNTs and CNFs exist, there haven’t been
any studies on the fracture performance of MWCNT and CNF mortar nanocomposites. The incorporation of fibers at the
nanoscale and their influence on the interfaces and the pore structure of the mortar matrix are likely to render significant
differences to the fracture response of the nanoreinforced mortars as compared to conventional ordinary Portland cement
(OPC) systems.
The objective of this study is to investigate the mechanical and fracture properties of MWCNT and CNF reinforced
mortars. Mortar nanocomposites reinforced with well dispersed MWCNTs and CNFs at an amount of 0.1 wt% of cement
were fabricated. A detailed investigation on the effect of the nanoscale fibers on the mechanical properties and fracture
toughness of the mortar matrix was performed by conducting three-point bending and fracture mechanics experiments.
Results compared with similarly fabricated reference mortars without the nano-reinforcement are clearly showing that the
incorporation of MWCNTs and CNFs in the mortar matrix significantly improves the mechanical and fracture properties of
the mortar matrix.

P.A. Danoglidis • M.G. Falara • M.K. Katotriotou • M.S. Konsta-Gdoutos • E.E. Gdoutos (*)
Department of Civil Engineering, Democritus University of Thrace, 12 Vas. Sofias, 671 00 Xanthi, Greece
e-mail: egdoutos@civil.duth.gr

# The Society for Experimental Mechanics, Inc. 2016 241

C. Ralph et al. (eds.), Mechanics of Composite and Multi-functional Materials, Volume 7,
Conference Proceedings of the Society for Experimental Mechanics Series, DOI 10.1007/978-3-319-21762-8_30
242 P.A. Danoglidis et al.

30.2 Experimental Program

30.2.1 Materials and Specimen Preparation

The material investigated was a cement-based composite with the matrix reinforced by MWCNTs or CNFs. Characteristic
properties of MWCNTs and CNFs are seen in Table 30.1. Values of an estimated number of MWCNTs or CNFs per unit
volume of the cementitious matrix are also included in Table 30.1, expressed as fiber count. Mortar specimens were prepared
at a water to cement ratio (w/c) of 0.485 and standard sand according to EN 196-1 at a sand to cement ratio (s/c) of 2.75.
Commercially available Type I ordinary Portland cement (OPC) was used for all mixes. To allow homogeneous dispersion
of MWCNTs and CNFs, suspensions were prepared by adding the MWCNTs or CNFs in an aqueous surfactant solution and
applying ultrasonication energy, following the method described in Konsta-Gdoutos and coworkers [2, 3]. The materials
were mixed according to ASTM 305. Two types of specimens were prepared: 40
40
160 mm prisms for the flexural
strength testing; and 20
20
80 mm notched beams for the determination of the fracture toughness. Following
demolding, the samples were cured in lime-saturated water for 3, 7, and 28 days.

30.2.2 Mechanical and Fracture Testing

The mechanical and fracture performance of the nanocomposites was evaluated by three point bending and notched three
point bending tests, respectively. Three point bending tests were conducted on 40
40
160 mm beams at the age of 3, 7
and 28 days, using a closed-loop MTS servohydraulic testing machine with a 25 kN capacity. The rate of displacement was
kept at 0.1 mm/min. The ASTM C348 was followed to determine the average values of the flexural strength and Young’s
modulus. Fracture mechanics tests were conducted on notched 20
20
80 mm prismatic specimens at the age of 3, 7 and
28 days, by the aforementioned experimental procedure. A 6 mm notch was introduced into the prismatic specimens using a
water-cooled band saw machine. To measure the crack mouth opening displacement (CMOD) a pair of knife edges is
attached at the two sides of a performed notch on the lower surface of the specimen. The crack mouth opening displacement
(CMOD) at the notch, set at a rate of 0.012 mm/min, was used as the feedback control signal for running the test. Young’s
modulus, and fracture toughness were calculated from the load-CMOD graphs as described in [9]. Specifically, the Young’s
modulus is expressed from the specimens’ compliance as:

6Sa0 g2 ða0 Þ
E ¼ ð30:1Þ
C i b2 t

where S, b, t and ao are specimens’ dimensions presenting in Fig. 30.1, Ci (mm/N) is the initial compliance calculated from
the load-CMOD curve and g2(ao) is the geometric function calculated as:

0:66
g2 ða0 Þ ¼ 0:76  2:28a0 þ 3:87a20  2:04a30 þ ð30:2Þ
ð1  a0 Þ2

Fracture toughness values were calculated using both the loading and unloading compliances according to the two-
parameter fracture model (TPFM) developed by Jenq and Shah [10].

Table 30.1 Properties and fiber count of MWCNTs and CNFs

Fiber type Diameter (nm) Length (μm) Purity (%) Surface area (m2/gr) Bulk density (gr/cm3) Aspect ratio Fiber count
MWCNTs 20–45 10 >98 >200 0.18 500 36.1
1010
CNFs 50–200 30–100 – 43 0.016–0.048 650 2.11
1010
30 MWCNT and CNF Cementitious Nanocomposites for Enhanced Strength and Toughness 243

b b

ao=b/3 ao

S=4b t

Fig. 30.1 Experimental setup of fracture mechanics test

14
w/c/s=0.485/1.0/2.75
12 12.23
Flexural strength (MPa)

11.09
10

6 5.94

4
Fiber count
M -
2 M+MWCNTs 0.1wt% 36.1x1010
M+CNFs 0.1wt% 2.11x1010
0
0 5 10 15 20 25 30
Days

Fig. 30.2 Flexural strength of mortar nanocomposites reinforced at an amount of 0.1 wt% of cement MWCNTs and CNFs

30.3 Results and Discussion

Results of the flexural strength and Young’s modulus of neat mortars and mortars reinforced with MWCNTs or CNFs at an
amount of 0.1 wt% by weight of cement at the age of 3, 7 and 28 days are presented in Fig. 30.2 and Table 30.2 respectively.
So far, results in the literature report either a decrease, or occasionally only a marginal increase in the flexural strength and
Young’s modulus of nanoreinforced cement pastes and mortars [11–14]. In our nanoreinforced mortars however, both the
flexural strength and Young’s modulus increase greatly, at all ages. More specifically, the 28 days nanocomposites
reinforced with MWCNTs or CNFs at amounts of 0.1 wt% exhibit a 86.7 % and 105.9 % increase in flexural strength and
92.4 % and 94.3 % increase in Young’s modulus, respectively. As it is depicted from Table 30.2 the Young’s modulus values
determined by the three point bending tests are consistent with the values determined by the fracture mechanics tests on
notched specimens. It is also observed that despite the fact that the CNF fiber count is much lower than the MWCNT count,
the flexural strength of the CNF nanocomposites is slightly higher than that of the MWCNT mixes. This can be explained by
the CNFs’ complex nanostructure. Their outer surface usually consists of conically shaped graphite planes canted with
respect to the longitudinal fiber axis [15, 16]. These edges, which are present along the circumference of the fiber, can be
used to help anchor the fiber in the matrix and prevent interfacial slip. Additionally, these edges provide the CNFs with a
higher reinforcing efficiency. As a result the CNF cementitious composites demonstrate the ability for higher load transfer
244 P.A. Danoglidis et al.

Table 30.2 Young’s modulus of MWCNT/CNF reinforced mortars

Age Young’s modulus (GPa) 40
40
160 mm Young’s modulus (GPa) notched 20
20
80 mm
M 3 9.18 9.89
7 10.83 12.00
28 13.52 14.28
M + MWCNTs 0.1 wt% 3 16.01 16.68
7 18.06 18.43
28 27.13 27.47
M + CNFs 0.1 wt% 3 11.75 12.21
7 16.98 16.86
28 27.08 27.74

450
Fiber count
400 M -
M+MWCNTs 0.1wt% 36.1x1010
350 M+CNFs 0.1wt% 2.11x1010
300
28d w/c/s=0.485/1/2.75
Load (N)

250
200
150
100
50
0
0.000 0.010 0.020 0.030 0.040 0.050 0.060 0.070 0.080 0.090 0.100
C.M.O.D. (mm)

Fig. 30.3 Load-CMOD curves for 28 day neat mortar and mortar reinforced with MWCNTs or CNFs at amount of 0.1 wt% of cement (Linear
elastic fracture mechanics)

efficiency, which is the key element that determines the mechanical response of the fiber nanocomposites. Typical load-
CMOD curves (following the linear elastic fracture mechanics) of OPC mortar specimens and specimens reinforced with
MWCNTs and CNFs at amount of 0.1 wt% of cement, are shown in Fig. 30.3. The load-CMOD response of the
nanocomposite mortars revealed an increase of the peak load as much as 65 % for the MWCNT and 89 % for the CNF
reinforced mortars compared to the neat mortar. Figure 30.4 shows the TPFM loading and unloading compliance curves for
the neat mortar and mortar nanocomposites that are used to determine the fracture toughness, KIC. The fracture toughness is
the most important parameter for the characterization of a material’s fracture properties. It gives a measure of the resistance
of a material to the growth of existing cracks. From Fig. 30.5 it is observed that the KIC values of both the MWCNT and CNF
nanocomposites are higher than the values of the neat mortar at all ages. Compared to the neat mortar the 28 days MWCNT
and CNF nanocomposites exhibited a 86.1 % and 119.4 % increase in fracture toughness, respectively.
30 MWCNT and CNF Cementitious Nanocomposites for Enhanced Strength and Toughness 245

450
28d w/c/s=0.485/1.0/2.75
400

350

300
Load (N)

250

200

150

100 Fiber count

M
-
50 M+MWCNTs 0.1 wt% 36.1x10
10
M+CNFs 0.1 wt% 2.11x10 10
0
0.000 0.005 0.010 0.015 0.020
C.M.O.D. (mm)

Fig. 30.4 Load-CMOD curves for 28 day neat mortar and mortar reinforced with MWCNTs or CNFs at amount of 0.1 wt% of cement
(Two-parameter fracture model)

1.8
w/c/s=0.485/1/2.75
1.6 1.58

1.4 1.34
KIC (MPaxÖm)

1.2

1.0

0.8 0.72

0.6

0.4 Fiber count

M -
0.2 M+MWCNTs 0.1wt% 36.1x1010
M+CNFs 0.1wt% 2.11x1010
0.0
0 5 10 15 20 25 30
Days

Fig. 30.5 Fracture toughness of OPC mortar and mortars reinforced at an amount of 0.1 wt% of cement MWCNTs and CNFs

30.4 Conclusions

A thorough investigation of the mechanical and fracture properties of cementitious nanocomposites reinforced with well
dispersed multiwall carbon nanotubes (MWCNTs) and carbon nanofibers (CNFs) was performed. Flexural strength and
Young’s modulus and critical fracture toughness were investigated and compared with similarly processed reference cement
based mixes without the nano-reinforcement. The excellent reinforcing capability of MWCNTs and CNFs is demonstrated
by a significant improvement in flexural strength (87 % for MWCNTs and 106 % for CNFs reinforcement), Young’s
modulus (100 %), and fracture toughness (86 % for MWCNTs and 119 % for CNFs reinforcement).
246 P.A. Danoglidis et al.

Acknowledgements The authors would like to acknowledge the financial support of the National Strategic Reference Framework (NSRF)
Research Funding Program “Thales-Democritus University of Thrace-Center for Multifunctional Nanocomposite Construction Materials”
(MIS379496) funded by the European Union (European Social Fund—ESF) and Greek national funds through the Operational Program
“Education and Lifelong Learning”.

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