Cement and Concrete Composites 70 (2016) 110e118

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Cement and Concrete Composites

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

Portland cement mortar nanocomposites at low carbon nanotube and

carbon nanofiber content: A fracture mechanics experimental study
Emmanuel E. Gdoutos, Maria S. Konsta-Gdoutos*, Panagiotis A. Danoglidis
Department of Civil Engineering, Democritus University of Thrace, Xanthi, Greece

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

Article history: A thorough fracture mechanics characterization of Portland cement mortars reinforced with multi wall
Received 20 August 2015 carbon nanotubes (MWCNTs) and carbon nanofibers (CNFs) took place. The critical values of stress in-
Received in revised form tensity factor, KSIC ; strain energy release rate, GSIC ; crack tip opening displacement, CTODc; and critical
23 March 2016
crack length, ac of 3, 7, and 28 days Portland cement mortars, reinforced with well dispersed carbon
Accepted 27 March 2016
nanotubes and carbon nanofibers were experimentally determined. Prismatic notched specimens of neat
Available online 30 March 2016
mortars and mortars reinforced with 0.1 wt.% CNFs, and 0.1 and 0.2 wt.% MWCNTs were subjected to a
three point closed loop bending test, using the crack mouth opening displacement, CMOD, as the
Keywords:
Mortars
feedback signal. The fracture parameters of the nanoreinforced mortars were then determined using the
Multi-walled carbon nanotubes two parameter fracture model. The excellent reinforcing and toughening efficiency of MWCNTs and CNFs
Carbon nanofibers is demonstrated by a significant improvement in the critical stress intensity factor/fracture toughness
Fracture toughness stress intensity factor (128.6%), critical strain energy release rate (154.9%), and critical crack tip opening displacement (39%).
Strain energy release rate These results allow us to conclude that the MWCNTs and CNFs beneficially alter the nanostructure of the
Modulus of elasticity mortar matrix, resulting to a significant enhancement of all fracture and mechanical properties and
provide the material, with the ability of performing multiple structural functions.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction cement pastes, there is practically no information available in the

literature on the determination of the fracture parameters such as
The most important properties a structural material can provide fracture toughness, or strain energy release rate of MWCNTs or
are strength, stiffness, fracture toughness, energy absorption CNFs reinforced cement pastes, mortars or concrete. Fracture me-
capability and ductility. Mortars and concrete are generally chanics characterization of cementitious materials is of great
considered as inherently brittle materials; for that reason it is importance for several reasons. First, it is generally accepted that
extremely difficult to improve simultaneously all four of the material separation is better described by energy principles rather
aforementioned structural properties. Multi wall carbon nanotubes than by stress or strain. During fracture, new material surfaces are
(MWCNTs) and carbon nanofibers (CNFs), with their supreme created in the material. The energy required to create new material
stiffness, high strength and aspect ratio are excellent reinforcing surfaces during the fracture process is a fundamental characteristic
candidate materials, offering unprecedented improvements in both quantity of the material: the evaluation of the fracture mechanics
strength and stiffness [1e3]. These fibers typically exhibit a Young's parameters provides a basis for the understanding of the fracture
modulus around 1 TPa, tensile strength of 65e93 GPa, and process. Second, the design of large structures, like dams and nu-
maximum strain of 10e15% [4]. Reinforcement at this scale, in clear reactors that behave in a rather brittle manner, as well as
addition to providing fracture resistance was found to beneficially applications of high strength concrete with compressive strength
alter the nanostructure of cement based materials [5]. higher than 100 MPa are benefited tremendously by fracture me-
However, whilst most studies so far concentrate in experimen- chanics: classical theories of fracture cannot explain the size effect,
tally determining the strength and the stiffness of nanoreinforced according to which the ultimate stress of geometrically similar
structures of different sizes depends on the size of the structure.
Moreover, the toughness as calculated by the area under the stress-
strain curve of the material cannot be used as a true material
* Corresponding author. property, since it is size and geometry dependent.
E-mail address: mkonsta@civil.duth.gr (M.S. Konsta-Gdoutos).

http://dx.doi.org/10.1016/j.cemconcomp.2016.03.010
0958-9465/© 2016 Elsevier Ltd. All rights reserved.
 E.E. Gdoutos et al. / Cement and Concrete Composites 70 (2016) 110e118 111

Direct application of fracture mechanics principles has been the critical energy release rate for high performance concrete,
used for the experimental determination of the critical fracture mortar, fiber reinforced concrete and masonry units. Other authors
toughness of cementitious materials. The foundations of the examined the fracture properties of mortars or concrete with fly
application of fracture mechanics to cementitious materials were ash, clay and metacaolin. Moukwa et al. [25] studied the effect of
laid down by the pioneering work of Hillerborg [6,7] who intro- alumino-silicate clays on the critical stress intensity factor and
duced the fictitious crack model of concrete, in an analogous way to CTODc. They concluded that appropriate use of silica fume and
the Dugdale-Barenblatt model of metals. The methodology has alumino-silicate clays can increase the ductility and strength of
been similar to the experimental determination of the critical strain cementitious materials. Das et al. [26] used notched three-point
energy release rate, GSIC , or stress intensity factor, KSIC , in metals bend specimens to determine the critical stress intensity factor
[8e10]. Notched three-point bend specimens have been most and critical crack tip opening displacement in mortars in which the
popular. The specimens were loaded to a progressively increasing ordinary Portland cement (OPC) was replaced by limestone or a
load and the load versus deflection of crack mouth opening combination of limestone and fly ash/metakaolin. The fracture
displacement (CMOD) response was recorded. The value of GSIC , or quantities were determined by using a two-parameter method and
KSIC , is determined from the peak load or the load at the intersection a non-contact digital image correlation. It was obtained that blends
with the secant of slope 95% of the initial slope and the initial notch of OPC replacement materials and limestone can lead to enhanced
length [11e15]. The values of GSIC , or KSIC obtained were dependent fracture mechanics properties and ductility. Sarker et al. [27]
on the size of the specimen and its geometrical configuration studied the fracture characteristics of geopolymer (GPC) and OPC
[10,11,15e18]. However, since the experimental values of the critical concrete using three-point bend specimens. They found that the
strain energy release rate are specimen size dependent they could critical stress intensity factor is higher for the GPC than the OPC
not be regarded as a characteristic material property. In both metal concrete. Nikbin et al. [28] studied the fracture characteristics of
and concrete structures, nonlinear zones of small (small scale self-compacting concrete using notched three-point bend speci-
yielding approximation is treated by linear elastic fracture me- mens. All the above results are summarized and compared with
chanics) or normal sizes (ductile fracture) develop at the crack tip results of this study in Table 1.
[19]. In ductile metals however, the material in the nonlinear It is the objective of the present work to provide a thorough
fracture process zone (FPZ) ahead of the crack tip undergoes fracture mechanics characterization through the experimental
hardening or perfect plasticity, whereas in concrete the material determination of the fracture parameters of nanomodified Portland
undergoes softening damage. In cementitious materials, within cement mortars, reinforced with well-dispersed MWCNTs and
FPZ, many micro-failure mechanisms including matrix micro- CNFs and demonstrate their superb reinforcing and toughening
cracking, debonding of cement-matrix interface, crack deviation effect. For this reason, three-point bending notched specimens of
and branching take place. All these mechanisms contribute to the
energy of fracture. The size of the FPZ ahead of the stress-free crack
Table 1
depends on the geometry and the size of the structure and the type
Comparison of the stress intensity factors of cement based materials.
of the material [20]. For cement paste the FPZ length is of the order
of a millimeter, for mortar is about 30 mm, for normal concrete Researchers KSIC (MPa
√m)
with medium aggregates is up to 500 mm, for dam concrete with Stynoski P. et al. [32] 0.41
extra large aggregates is about 3 m, for a grouted soil mass is w/c/s ¼ 0.485/1.0/2.75
around 10 m and in a mountain and jointed rock values of 50 m may 25  25  125 mm
7 mm notch (ao/W ¼ 0.28)
be typical. On the other hand, the length of the FPZ in a fine-grained 28 d
silicon ozide ceramic is of the order of 0.1 mm, and in a silicon wafer Reda Taha M.M. et al. [33] 1.00
of the order of 10e100 nm. Hence, direct application of linear normal strength mortar (MTR)
elastic fracture mechanics for the characterization of the fracture 100  75  350 mm
25 mm notch (ao/W ¼ 0.25)
behavior of cementitious materials may lead to erroneous results.
28 d
One method developed to account for the FPZ in concrete materials Moukwa M. et al. [35] 0.85
is the Two-Parameter Fracture Method (TPFM) developed by Jenq w/c/s ¼ 0.3/1.0/2.6
and Shah [21]. The method takes into account that a change in 75  75  200 mm
specimen compliance can be correlated to the length of the effec- 25 mm notch (ao/W ¼ 0.3)
28 d
tive crack. This effective crack length takes into consideration the Das S. et al. [36] 0.88
inelastic phenomena that take place in the FPZ ahead of the crack water/powder ¼ 0.4
tip at the critical (i.e., peak) load. 76  25  330 mm
To the authors' knowledge only one reference [22] exists in the 19 mm notch (ao/W ¼ 0.25)
28 d
literature on the experimental determination of the fracture pa-
Sarker P.K. et al. [37] 0.52
rameters of concrete or mortars reinforced with MWCNTs using the w/c/s ¼ 0.47/1.0/2.61
TPFM. Stynoski et al. studied the fracture properties of various 100  100  600 mm
Portland cement mortars containing silica fume, carbon nanotubes 25 mm notch (ao/W ¼ 0.25)
and carbon fibers using notched three-point bend specimens and 28 d
Nikbin I.M. et al. [38] 1.12
the TPFM. They observed that carbon nanotubes provided a slight w/c/s ¼ 0.48/1.0/5.0
improvement in flexural strength and fracture toughness of about Shah S.P. et al. [14] 0.89
5e10% at 7 and 28 days of age. Their effect on critical crack tip w/c/s ¼ 0.45/1.0/2.6
opening displacement (CTODc) was more significant, achieving a 76  28.6  305 mm
25 mm notch (ao/W ¼ 0.3)
20% improvement at 28 days. Using silica fume and carbon nano-
90 d
tubes together, a significant improvement in toughness and CTODc Gdoutos E.E. et al. [Present work] 0.72
of about 35% and 56% after 28 days was observed. w/c/s ¼ 0.485/1.0/2.75
Some information exists on the fracture properties of micro- 20  20  80 mm
fiber reinforced concrete. Taha et al. [23] used the effective crack 6 mm notch (ao/W ¼ 0.3)
28 d
model developed by Karihaloo and Nallathambi [24] to determine
112 E.E. Gdoutos et al. / Cement and Concrete Composites 70 (2016) 110e118

OPC mortars reinforced with 0.1 wt.% CNFs, and 0.1 and 0.2 wt.% of band saw machine. The length of the notch was calculated based
cement MWCNTs were manufactured and tested under servo- on the RILEM standard, which requires a notch to depth ratio of
hydraulic controlled conditions using the CMOD as the feedback close to 1/3.
signal. The fracture parameters of the nanoreinforced mortars were
then determined by following the two parameter model by Jenq
and Shah [21]. The exceptional reinforcing and toughening capa- 2.2. Experimental determination of fracture parameters
bility of MWCNTs and CNFs is demonstrated by a significant
improvement in the critical values of stress intensity factor The two-parameter fracture model [21] was used to obtain the
(128.6%), strain energy release rate (154.9%), crack tip opening fracture mechanics properties of the specimens from the experi-
displacement (39.7%) and effective crack length (10.3%), resulting in mental results. These properties include the critical values of the
advanced materials for civil engineering applications with stress intensity factorKSIC, the strain energy release rate, GSIC , the
increased strength, stiffness and toughness. crack tip opening displacement, CTODc, the crack length, ac, and the
material length, Q. The basic idea behind the method is to deter-
mine an effective, not the initial, crack length. This length takes into
2. Experimental work
consideration the inelastic phenomena that take place in the frac-
ture process zone ahead of the crack tip. The effective crack length
2.1. Materials and specimens
is equal to the actual crack length plus the length of the fracture
process zone. For the application of the method the relationship
In this study Type I ordinary Portland cement (OPC) 42.5 R and
between the compliance, defined as the value of the crack tip
standard sand according to EN 196-1 were used for casting the
opening displacement per unit load, and the crack length for special
mortar specimens. The characteristic properties of the nano-
three-point notched bend specimens is established. The unloading
reinforcement (MWCNTs and CNFs) are shown in Table 2. Values of
compliance of the specimen is determined by unloading the
an estimated fiber count, the number of fibers (in this case
specimen after reaching the peak load. The effective crack length is
MWCNTs and CNFs), which are theoretically evenly distributed in a
calculated from the relationship between the compliance and the
unit volume of the matrix, assuming perfect dispersion, according
crack length using the unloading compliance. The critical value of
to ACI 544.1R-96: Report on Fiber Reinforced Concrete [29] is also
strain energy release rate, GSIC , or stress intensity factor, KSIC , is
included in Table 3. As MWCNTs and CNFs adhere together due to
calculated from the peak load and the effective crack length using
van der Waals forces, agglomerates or bundles are formed that
linear elastic fracture mechanics formulas. It has been established
make their dispersion difficult and laborious. Early attempts to add
that KSIC determined in this way is independent of the specimen
MWCNTs to cementitious materials did not produce impressive
type and size, thus a true material property. Determination of KSIC
results, mainly due to an incomplete and insufficient dispersion
needs two quantities measured from the test, the unloading
that resulted to poor adhesion [30e36]. In this work, effective
compliance and the peak load. Simultaneously with KSIC the
dispersion of the nanoscale fibers was achieved following the
modulus of elasticity and the critical value of the crack tip opening
method of Konsta-Gdoutos and coworkers previously applied in
displacement are determined.
cement pastes [1,5,37e40]. The authors tested notched three point
The experimental determination of the above quantities is based
bending cement paste specimens and found that small amounts of
on the load versus CMOD curve for a loading-unloading cycle of a
successfully dispersed MWCNTs (0.025e0.08 wt% of cement)
three-point bend specimen (Fig. 1). From the curve the following
greatly increase the flexural strength and stiffness of the nano-
quantities are measured: The compliances for the loading and
reinforced pastes: modulus of elasticity increases by z45%; while
unloading parts, and the maximum load.
the flexural strength increased by z25% for a reinforcement of
The modulus of elasticity, E, is calculated by:
0.08 wt% of cement. In a typical dispersion procedure MWCNT/CNF
suspensions are prepared by adding the nanofibers to an aqueous 6Sao g2 ðao Þ
polycarboxylate based surfactant solution, at a surfactant to E¼ (1)
nanofibers weight ratio of 4.0. Ultrasonic energy is applied to the
Ci b2 t
suspensions by a 500 W cup-horn high intensity ultrasonic pro-
where: Ci ¼ the compliance of the loading part of the loadeCMOD
cessor with a standard probe of a diameter of 19 mm and a tem-
curve, a0 ¼ (a0 þ HO)/(b þ HO), a0 ¼ crack length, S ¼ span length,
perature controller. The sonicator is operated at amplitude of 57%
b ¼ specimen depth, t ¼ specimen thickness, HO ¼ length defined
so as to deliver constant energy rate of 1900e2100 J/min, at cycles
in Fig. 2, g2 (a0) ¼ geometric function defined by
of 20 s in order to prevent overheating of the suspensions.
After completion of the sonication process, the MWCNT/CNF 0:66
suspensions were added into the OPC and sand at a constant water g2 ðao Þ ¼ 0:76  2:28ao þ 3:87a2o  2:04a3o þ (2)
ð1  ao Þ2
to cement ratio w/c ¼ 0.485 and sand to cement ratio s/c ¼ 2.75.
Mixing of the materials was performed according to procedure In a similar way, the modulus of elasticity E is calculated from
outlined by ASTM 305 using a standard robust mixer capable of the compliance of the unloading part of the load-CMOD curve as
operating from 140 ± 5 revolutions per minute (r/min) to 285 ± 10 r/
min. After mixing, the mixtures were cast in 20  20  80 mm oiled 6Sac g2 ðac Þ
E¼ (3)
molds. Following demolding, the samples were cured in lime- Cu b 2 t
saturated water until testing. A 6 mm notch was introduced into
the prismatic 20  20  80 mm specimens using a water-cooled where:

Table 2
Properties of MWCNTs and CNFs.

Fiber type Diameter (nm) Length (mm) Surface area (m2/gr) Bulk density (gr/cm3) Aspect ratio

MWCNTs 20e45 10 >200 0.18 307

CNFs 100 50e200 43 0.016e0.048 1250
 E.E. Gdoutos et al. / Cement and Concrete Composites 70 (2016) 110e118 113

Table 3
Fiber count, fracture load and Young's modulus of 28 days neat mortars and mortar nanocomposites reinforced with well dispersed MWCNTs and CNFs.

Fiber count Fracture load (kN) 40  40  160 mm 3 point Young's Modulus (GPa) Young's Modulus (GPa) 40  40  160 mm 3
bending 20  20  80 mm LEFM point bending

M e 1.58 14.3 13.5

M þ MWCNTs 3.61  1011 2.96 27.5 27.1
0.1 wt.%
M þ MWCNTs 7.22  1011 2.47 23.3 23.0
0.2 wt.%
10
M þ CNFs 0.1 wt.% 1.69  10 3.26 27.7 27.6

Cu ¼ the compliance of the unloading part of the loadeCMOD The material length Q is proportional to the size of the fracture
curve, ac ¼ the effective crack length, ac ¼ (ac þ HO)/(b þ HO). process zone, and can be used to characterize the brittleness of the
The unloading compliance is taken within 95% of the peak load material. The smaller the value of Q the more brittle the material is.
calculated from the load-CMOD curve. The value of the effective It was found that values of Q are in the range of 12.5e50 mm for
crack length ac is calculated by equating the values of the modulus hardened cement paste, 50e150 for mortar, and 150e350 for
of elasticity E defined from Eqs (1) and (3). This results in the concrete.
following equation Prismatic notched specimens 20  20  80 mm were tested in
three point bending at ages of 3, 7 and 28 days. The test was per-
Cu g2 ðao Þ formed using a 25 kN MTS servo-hydraulic, closed-loop testing
ac ¼ ao (4) machine under displacement control. The CMOD was used as the
Ci g2 ðac Þ
feedback signal to produce stable crack propagation at the rate of
Equation (4) is solved numerically for the determination of the 0.008 mm/min, such that the peak load is reached in about 5 min.
critical crack length ac. The specimens were monotonically loaded up to the maximum
The critical stress intensity factor is calculated by the equation load. The applied load is then manually reduced after the load
passed the maximum load and within the 95% of the maximum
pffiffiffiffiffiffiffiffi  
load. Both loading and unloading compliances and the peak load
S pac g1 ac=b
KSIC ¼ 3ðPcr þWh Þ (5) were monitored during the test. The load versus CMOD data values
2b2 t were continuously recorded during testing. The specimens that
result in strengths differing by more than 10% from the average
where: value of all test specimens made from the same sample and tested
Pc ¼ the peak load, Wh ¼ Who S/L, Who ¼ the self weight of the at the same period were not considered in determining the fracture
beam, and

h i
a  1:99  ðac =bÞð1  ac =bÞ 2:15  3:93ðac =bÞ þ 2:70ðac =bÞ2
c
g1 ¼ pffiffiffiffi (6)
b pð1 þ 2ac =bÞð1  ac =bÞ3=2

The critical strain energy release rate is calculated by: properties. After discarding the strength values, if less than two
strength values were left for determining the fracture properties at
 2 any given period a retest was made. The above mentioned proce-
KSIC dure is routinely followed to ensure that the variation of the test
GSIC ¼ (7) results does not affect the experimentally determined values of the
E
measured quantities.
The critical crack tip opening displacement is calculated

6ðPc þ 0:5Wh ÞSac g2 ðac =bÞ h 2

 ac  i1=2
CTODc ¼ 2
, ð1  bο Þ þ 1:081  1:149 bο  b2o (8)
Eb t b

by:where: 3. Results and discussions

b0 ¼ a0/ac, g2 (ac/b) is calculated from Eq. (2) with a0 ¼ ac/b.
Based on the values of KSIC and CTODc, Jenq and Shah introduced Load-CMOD curves from neat mortar and mortar nano-
a material length, Q, by composites reinforced with MWCNTs at an amount of 0.1 wt.% of
cement, obtained from the linear elastic fracture mechanics test are
!2 shown in Fig. 3. The load-CMOD curves of both the neat mortar and
E CTODc
Q¼ (9) the 0.1 wt.% MWCNT reinforced mortar show the same pattern,
KSIC consisting of a linear elastic stage before crack initiation, nonlinear
114 E.E. Gdoutos et al. / Cement and Concrete Composites 70 (2016) 110e118

350 400
M
300 350 M+MWCNTs 0.1wt%
Pc
250 300
200 250
P (N)

Load (N)
150 Ci 200
100 Unloading M+MWCNTs 0.2 wt%
at peak load 150
TPFM
50 Cu 28d 100
0
50
0.000 0.005 0.010 0.015 0.020 0.025 0.030
0
CMODcp CMODec 0.000 0.010 0.020 0.030 0.040 0.050 0.060
C.M.O.D. (mm) C.M.O.D. (mm)

Fig. 1. Typical load-CMOD curve showing the loading and unloading procedure for a Fig. 3. Load-CMOD curves for a 28 d neat mortar and a mortar reinforced with
28 d mortar reinforced with well dispersed MWCNTs at an amount of 0.2 wt.% of MWCNTs at an amount of 0.1wt.% of cement
cement.

stage of stable crack propagation preceding unstable failure and

unstable extension stage after the peak load. It is observed how-
ever, that the peak value of the load-CMOD curve of the 0.1 wt.%
MWCNT nanocomposite is higher compared to the neat mortar,
therefore the ultimate fracture load is also higher. Moreover, as
shown from Table 3, the ultimate fracture load of the 0.1 wt.% CNF
mortar is also higher compared to both the neat mortar and the
0.1 wt.% MWCNT nanocomposite. Table 3 also provides the Young's
modulus of both 0.1 and 0.2 wt.% MWCNT and the 0.1 wt.% CNF
nanocomposites, all of which are higher compared to the neat
mortar. It is of interest to note here that the values of Young's
modulus of Table 3 were obtained from two different tests: 3 point
bending test on 4  4  16 cm specimens; and fracture mechanics
test on 2  2  8 cm notched specimens.
Fig. 4. Effective crack length of 28 d neat mortar and mortars reinforced with 0.1 wt.%
A thorough fracture mechanics characterization of cement
and 0.2 wt.% of cement MWCNTs
based materials using the TPFM typically requires determination of
the critical values of the crack length (ac), stress intensity factor
(KSIC ), strain energy release rate (GSIC ), and crack tip opening 28 days of hydration, for neat mortar and mortars reinforced with
displacement (CTODC). This way, failure by crack propagation can MWCNTs at amounts of 0.1 wt.% and 0.2 wt.% of cement. The
be described when stress intensity factor, strain energy release rate fracture toughness KSIC is perhaps the most important parameter for
or crack mouth/crack tip opening displacement reach their critical characterizing a material's resistance to cracking. As expected, the
values. The above mentioned quantities are functions of applied effect of the MWCNTs on the mortar matrix was significant: it is
loads, the material, size and dimensions of the specimen, while observed that KSIC increases with time for all three mixes. Addition
their critical values are true material properties. As discussed of MWCNTs significantly increases the toughness of the nano-
earlier the critical value of the stress intensity factor is calculated reinforced mortars at all ages. Specifically, the incorporation to the
from the peak load and the effective crack length using LEFM. The plain mortar of this very low dosage of 0.1%wt. MWCNTs resulted in
effective crack length is the sum of the initial notch plus the length an increase in the 28 d critical stress intensity factor/fracture
of the fracture process zone at the peak load. The effective crack toughness of 85.7%. This is the effect of an enhanced crack arresting
length, ac, values for the plain, 0.1 and 0.2 wt.% MWCNT reinforced at the nanoscale, which leads to a controlled coalescing process of
mortars were calculated directly from equation (4). Results of the cracking at the nano- and micro scale and allows the material to
28 d values are plotted in Fig. 4. An increase of z9.5% was observed greatly improve its toughness and mechanical performance. At this
for the 0.1%MWCNT nanoreinforced mortar over the plain one. A point, it should be mentioned that the quality and degree of
more modest increase (7%) was observed for the 0.2 wt.% MWCNT dispersion is the key for the successful enhancement of the fracture
mortar. Fig. 5 presents the values of the fracture toughnessKSIC , up to toughness and modulus of elasticity of the mortar matrix. To

Fig. 2. Experimental setup for the TPFM testing

 E.E. Gdoutos et al. / Cement and Concrete Composites 70 (2016) 110e118 115

1.6 70
66.0
1.4 60
1.3
54.1
1.2 50
KSIC (MPa√m)

1.1
1.0

GIC (N/mm)
40
35.3
0.8
0.7 30
0.6

S
20
0.4
M 10 M
0.2 M+MWCNTs 0.1wt% M+MWCNTs 0.1wt%
M+MWCNTs 0.2wt% M+MWCNTs 0.2wt%
0.0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
3d 7d 3d 7d 28d
Days 28d
Days
Fig. 5. Critical stress intensity factor, KIc, of neat mortar and mortar reinforced with
Fig. 7. Strain energy release rate of neat mortar and mortars reinforced with MWCNTs
MWCNTs at amounts of 0.1 wt.% and 0.2 wt.% of cement versus time for up to 28 days.
at amounts of 0.1 wt.% and 0.2 wt.% of cement up to 28 days of hydration.

further elucidate this, besides the fracture mechanics tests con-

0.0145
ducted on notched 2  2  8 cm specimens, three point bending
+18.6%
tests were also conducted on 4  4  16 cm prisms. Experimental 0.0140
values confirmed that the 0.1 wt.% MWCNT reinforced mortars
exhibit a fracture load of 2.96 kN, resulting in a flexural strength of 0.0135

CTODc (mm)
10.4 MPa, and a Young's modulus of 27.5 GPa. These values are 0.0130 +11.0%
approximately 86.7% and 92.4% respectively higher than the ones of
the neat mortar. A summary of these results can be found in Table 3. 0.0125
From the table it can also be seen that when compared to the
0.0120
0.1 wt.% reinforced mortars the peak load and Young's modulus
values of the 0.2 wt.% nanoreinforced mortars are slightly lower. M
0.0115 M+MWCNTs 0.1 wt%
Interestingly, and despite the fact that the estimated MWCNT count M+MWCNTs 0.2 wt%
(Table 3), that is the number of individual carbon nanotubes, is 0.0110
M M+MWCNTs M+MWCNTs
twice as much (7.22  1011) as the 0.1 wt.% MWCNT mortar the 0.1wt% 0.2 wt%
Young's modulus of the 0.2 wt.% mortar is 18.0% lower than the
Young's modulus of the corresponding 0.1 wt.% mix. This finding is Fig. 8. Critical crack tip opening displacement of 28 d neat mortar and mortars rein-
in good agreement with previous studies by the same authors on forced with 0.1 wt.% and 0.2 wt.% of cement MWCNTs.
carbon nanotube reinforced cement pastes [1,5]. Furthermore, it is
also observed that the value of KSIC is also lower for the 0.2 wt.%
degree of dispersion of these MWCNTs in loadings higher than
MWCNT reinforced mortar when compared to the 0.1 wt.% one. As
0.1 wt.% is slightly lower. Fig. 6 shows pictures of suspensions
discussed earlier, the reinforcing effect of the MWCNTs at the
prepared with 0.1 and 0.2 wt.% of cement MWCNTs. Some small
nanoscale mainly depends on the degree of dispersion within the
agglomerates can be seen on the 0.2 wt.% suspension container's
matrix [5]. Dispersion is a procedure that depends on many factors
walls. These inclusions act as stress concentration areas, leading to
such as the aspect ratio and concentration of the CNTs, intensity of
a degrade of both the mechanical and fracture properties of the
the energy supplied, type of surfactant etc. It is possible that the
nanoreinforced mortar. Nevertheless, analogous results are
observed for the critical strain energy release rate, GSIC , and the
critical crack tip opening displacement, CTODc, shown in Figs. 7 and
8 respectively. GSIC is considered the energy necessary for crack
initiation. As MWCNTs enhance the material's ability to control the
coalescence of cracks at the nano scale and the subsequent for-
mation of the microcracks, a higher amount of energy is required to
initiate cracking. Hence, the critical strain energy release rate
values are higher for both nanoreinforced mortars. Especially, for
the 0.1 wt.% MWCNT nanomodified mortars an impressive increase
of 87.0% is observed over the plain one. On the other hand, a higher
loading of MWCNTs slightly decreases the GSIC values, confirming
the trend already observed for the toughness values.
The exact same trend was observed for the critical crack tip
opening displacement CTODc values for all mixes. CTODc, similarly
to the stress intensity factor, is considered a geometry independent
fracture parameter when determined using the TPFM and can be
estimated from the peak load and the effective crack length. As
shown in Fig. 8, the 28 d CTODc values of the MWCNT reinforced
mortars are higher than the plain mortar ones. The markers in the
graph indicate the low and high values in the determination of
CTODc. However, while the critical value of the crack tip opening
Fig. 6. Pictures of 0.1% and 0.2%wt MWCNT sonicated suspensions
116 E.E. Gdoutos et al. / Cement and Concrete Composites 70 (2016) 110e118

that the estimated fiber count of the MWCNT reinforced mortars is

21 times higher than this of the CNF mortars (1.69  1010) (see
Table 3), the 28 d stress intensity factor of the CNF mortar is z23%
higher than the MWCNT one and 128.6% higher over the plain
mortar. The 28 d CNF nanocomposites also exhibit a tremendous
increase of strain energy release rate of 154.9% compared to the
plain mortar. Nevertheless, several parameters besides dispersion
are considered to improve both the fracture toughness and the
energy dissipated during fracture of the nanocomposites. These
parameters include the diameter and the length of the carbon fibers
at the nanoscale and the strength of CNT/CNF-mortar matrix
interfacial characteristics [41,42]. Taking into account that the load
bearing capacity of both MWCNTs and CNFs is large enough, it is
possible that the bigger diameter and length of the CNFs, along
with the extended graphite planes that exist in the outer CNF
Fig. 9. Effective crack length of 28 d neat mortar and mortars reinforced with 0.1wt.% surface [39], create a stronger interfacial bonding between the
of cement MWCNTs and CNFs. mortar matrix and the carbon nanofibers that enhances the
observed toughening effect. As a result the ultimate fracture load,
and consequently the flexural strength, and the Young's modulus of
1.8
0.1 wt.% CNF mortars also presented an impressive increase of
1.6 1.6 105.9% and 94.3%, respectively, when compared to those exhibited
1.4 1.3 from the meat mortar, (Table 3). Furthermore, the amount of the
1.2 energy required for crack initiation, expressed as the strain energy
KIC (MPax√m)

release rate is also higher. A similar trend was observed for the 28 d
1.0
of the CTODc values shown in Fig. 12, where a 39.0% increase of
0.8
0.7 CTODc was obtained from the 0.1 wt.% CNF nanocomposites over
S

0.6 the plain mortar.

0.4 As the critical values of the stress intensity factor and the crack
M
0.2 M+MWCNTs 0.1wt% tip opening displacement, and the modulus of elasticity were
M+CNFs 0.1wt% evaluated for all nanoreinforced mortars the material length Q was
0.0
0 5 10 15 20 25 30 calculated as well using Equation (9). As mentioned before, the
3d 7d 28d material length Q is proportional to the size of the fracture process
Days zone for the same material, and can be used to characterize the
brittleness of the material. Results of the 28 d calculated materials
Fig. 10. Stress intensity factors of neat mortar and mortars reinforced with MWCNTs or
CNFs at an amount of 0.1 wt.% of cement at 3, 7 and 28 days length values for the MWCNTs mixes are shown in Fig. 13. A com-
parison of the values of the 0.1% MWCNT and CNF mixes is also
shown in Fig. 13. As can be seen from Table 3, both the peak loads of
displacement for the 0.1% MWCNT mortar is 18.6% higher over the the MWCNT and CNF reinforced mortars are higher than the peak
plain mortar, the 0.2% mix exhibits lower CTOD values at peak load. load of the plain mortar. The substantial increase in the modulus of
Results of the calculated values of the effective crack length ac, at elasticity is also typical for mortars reinforced with well dispersed
28 days for the plain, 0.1 wt.% MWCNT and 0.1 wt.% CNF reinforced MWCNTs and CNFs. The strong interfaces between the mortar
mortars are shown in Fig. 9. A very modest increase of z1.7% was matrix and the carbon fibers at the nanoscale greatly enhance both
observed for the 0.1% CNF nanoreinforced mortar over the 0.1% strength and stiffness. However, as flexural strength and stiffness
MWCNT one. A comparison of the fracture toughness valuesKSIC , for increase so does the toughness and the fracture energy. In fact, the
mortars nanomodified with 0.1 wt.% MWCNTs and CNFs at 3, 7 and toughness values of these nanoreinforced mixes are more than
28 days is shown in Fig. 10. Strain energy release rate values of the 100% higher over the plain mortar ones. As a result, the brittleness
same mixes are shown in Fig. 11. Interestingly, and despite the fact index values of both the 0.1% wt. MWCNT and CNF reinforced
mortars are higher; therefore both mixes exhibit a less brittle
behavior. Furthermore, it is also observed that the brittleness index
100
Q of the 28 d 0.1 wt.% MWCNT mix is higher than the 0.2 wt.% one;
90 90.0
therefore the 0.2% MWCNT reinforced mortars exhibit a more
80 brittle behavior than the 0.1% ones, mainly due to a lower degree of
70 66.0
dispersion.
GICS (N/mm)

60
50 4. Conclusions
40 35.3

30 A thorough fracture mechanics characterization of Portland

20 M
cement mortars reinforced with MWCNTs and CNFs took place. The
10 M+MWCNTs 0.1wt% critical stress intensity factor,KSIC ; the critical strain energy release
M+CNFs 0.1wt%
0 rate, GSIC ; and the critical crack tip opening displacement, CTODc of
0 5 10 15 20 25 30 3, 7, and 28 days Portland cement mortars, reinforced with well
3d 7d 28d
dispersed 0.1% and 0.2% wt. MWCNTs and 0.1% wt. CNFs were
Days
experimentally determined using the TPFM. The reinforcing and
Fig. 11. Strain energy release rate values of neat mortar and mortars reinforced with toughening effect of the MWCNTs and CNFs on the mortar matrix is
MWCNTs or CNFs at amount of 0.1 wt.% of cement up to 28 days of hydration. of utmost importance. The addition of this very low dosage of 0.1%
 E.E. Gdoutos et al. / Cement and Concrete Composites 70 (2016) 110e118 117

Fig. 12. Critical crack tip opening displacement of 28d neat mortar and mortars reinforced with 0.1 wt.% of cement MWCNTs and CNFs

90 105.9%; modulus of elasticity of 94.3%; stress intensity factor/frac-

80.7 83.0
80
ture toughness of 128.6%; critical strain energy release rate of
73.3 154.9%; and CTODc of 39%.
70
The strong interfaces between the mortar matrix and well
60 57.1
dispersed carbon fibers at the nanoscale substantially enhance both
Q (mm)

50 strength and stiffness. The evaluation however of the fracture pa-

40 rameters of the nanoreinforced mortars indicated that besides
30 strength and stiffness the values of toughness and fracture energy
20 are approximately 85e100% higher over the plain mortar. As a
result the material length values Q, as calculated using the TPFM, of
10
both the 0.1% wt. MWCNT and CNF reinforced mortars are higher
0
M M+MWCNTs M+MWCNTs M+CNFs than those of plain mortar; therefore both nanoreinforced mixes
0.1 wt% 0.2 wt% 0.1 wt% exhibit a less brittle behavior.

Fig. 13. Material length Q of 28d neat mortar and mortars reinforced with 0.1 wt.% and
0.2 wt.% of cement MWCNTs and 0.1 wt.% of cement CNFs Acknowledgements

This work was partially supported by the National Strategic

wt. MWCNTs to the plain mortar resulted in an increase in the 28 d Reference Framework (NSRF)eResearch Funding Program “Thales-
flexural strength of 86.7%; modulus of elasticity of 92.4%; critical Democritus University of Thrace-Center for Multifunctional Nano-
stress intensity factor/fracture toughness of 85.7%; critical strain composite Construction Materials” (MIS 379496) funded by the
energy release rate of 87.0%; and CTODc of 18.6%. A higher loading European Union (European Social Fund e ESF) and Greek national
of MWCNTs, with twice as much fiber count, exhibits an 18.0% funds through the Operational Program “Education and Lifelong
lower 28 d Young's modulus than this of the corresponding 0.1 wt.% Learning”. TITAN Inc., Glonatech Inc. and Sika Hellas Inc. are kindly
mix, mainly due to the presence of MWCNT agglomerates in the acknowledged for supplying the cement/sand, MWCNTs and sur-
mix, which act as stress concentration areas, leading to a degrade of factant respectively. The help provided by the Ph.D. student of the
both the mechanical and fracture properties of the nanoreinforced Lab. of Applied Mechanics of DUTh, M. Falara is greatly appreciated.
mortar. As a result the 0.2%wt. MWCNTs mortar mix exhibits a
slight decrease in the toughness, GSIC , and CTODc values.
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