Cement and Concrete Composites 82 (2017) 137e151

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Cement and Concrete Composites

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

Fresh and mechanical properties, and strain sensing of nanomodified

cement mortars: The effects of MWCNT aspect ratio, density and
functionalization
Maria S. Konsta-Gdoutos a, *, Panagiotis A. Danoglidis a, Maria G. Falara a,
Stephanos F. Nitodas b
a
Department of Civil Engineering, Democritus University of Thrace, Xanthi, Greece
b
Glonatech S.A. TE.S.P.A “Lefkippos” Ag. Paraskevi, GR-15341, Attica, Greece

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

Article history: A comprehensive analysis on the effect of aspect ratio, bulk density and functionalization of multi walled
Received 12 December 2016 carbon nanotubes (MWCNTs) in the development of nanomodified mortars, reinforced with different
Received in revised form types of MWCNTs is presented herein. A structural characterization of the pristine and functionalized
11 May 2017
carbon nanotubes was carried out with scanning electron microscopy (SEM), transmission electron
Accepted 12 May 2017
Available online 12 May 2017
microscopy (TEM), and thermogravimetric analysis (TGA). A simple one step dispersion method,
involving the application of ultrasonic energy and the use of a superplasticizer (SP) was utilized for the
preparation of uniformly dispersed MWCNT suspensions. The experimental determination of the fresh
Keywords:
Mortars
and 28d mechanical properties of mortars with w/c ¼ 0.5 and s/c ¼ 3.0, using four different types of well
Carbon nanotubes dispersed pristine and functionalized MWCNTs at an amount of 0.1 wt% of cement took place through: (i)
Functionalization flow and time of setting tests; (ii) three point bending experiments on 4  4  16 cm specimens; and (iii)
Bulk density uniaxial compression on the half prisms of the flexural test specimens (4  4  8 cm). The piezoresistive
Aspect ratio behavior of the mortars reinforced with the pristine MWCNTs was experimentally determined using the
Flexural strength 4-pole method, and compared with the strain sensing ability of the mortars reinforced with the func-
Stiffness tionalized MWCNTs. All MWCNT reinforced mortars exhibit a remarkable enhancement in the me-
Toughness
chanical properties. However, the 28d flexural strength, young's modulus and energy absorption
Strain sensing
capability of the mortars reinforced with the mechanically functionalized MWCNTs at an amount of
0.1 wt% increased by 120%, 124%, and 103% respectively. Finally, depending on the procedure of the
functionalization, chemical or mechanical, a different effect on the intrinsic properties of MWCNTs was
observed. The carboxylic groups attached to the surface of the chemically functionalized MWCNTs
indeed provided them with the ability of a uniform and effective dispersion, without the need of a
sonication procedure. On the other hand, it was found that functionalized MWCNTs do not always retain
the electrical properties of pristine MWCNTs.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction high aspect ratio make them ideal reinforcing materials, offering
outstanding improvement to the mechanical and electrical prop-
Carbon nanotubes (CNTs) exhibit outstanding mechanical erties of cementitious matrices that are being used in structural
properties such as a tensile strength of 65e93 GPa and a stiffness of applications [4e7].
about 1 TPa [1]. Their particular graphene electronic structure al- Earlier results in the literature suggest that multiwall carbon
lows them to exhibit semi-conducting, as well as quasi-metallic nanotubes (MWCNTs) fundamentally modify the nanostructure of
and metallic behavior [2,3]. All these, in combination with their cement based materials, by increasing the amount of high stiffness
C-S-H and reducing nanoporosity [8]. To unlock the nanotubes'
contribution in potential applications it is necessary to take into
account the differences in their geometrical and physical charac-
* Corresponding author. teristics, and structure. As extensively reviewed in the literature,
E-mail address: [email protected] (M.S. Konsta-Gdoutos).

http://dx.doi.org/10.1016/j.cemconcomp.2017.05.004
0958-9465/© 2017 Elsevier Ltd. All rights reserved.
138 M.S. Konsta-Gdoutos et al. / Cement and Concrete Composites 82 (2017) 137e151

MWCNTs consist of two or more concentric cylindrical shells of high strain-rate loading. Marginal improvement and/or decrease in
graphene sheets, coaxially arranged around a central hollow core. compressive and tensile strength were observed for quasi static
MWCNTs have a high aspect ratio, low bulk density and an loading. Collins et al. [20] reported the results of MWCNT disper-
extended specific area, which is of particular interest for adsorption sion on the consistency and strength of MWCNTeOPC pastes. The
and reactions taking place on the nanotubes' surface [9,10]. The authors observed a small variation in the measured mini-slump
interface length and strength depend directly on the geometrical values which however correspond to the variation in the aspect
characteristics of the nanotubes, hence a higher aspect ratio is ratio. The compressive strength results showed little variation be-
required for an effective transfer load between from the matrix to tween samples containing MWCNTs having almost the same aspect
the nanotube [11]. Another important parameter affecting the ratio. A remarkable increase was observed in the nanocomposite
properties of the MWCNT reinforced cementitious materials is the reinforced with a significantly lower aspect ratio MWCNTs. Abu Al-
dispersion of MWCNTs, which has proven a challenging and rather Rub et al. [21] investigated the reinforcing effect of two different
inconsistent procedure, primarily due to their inherent hydropho- types of MWCNTs (short and long) on the flexural strength, stiffness
bic nature and the strong van der Waals forces that cause entan- and toughness of nanomodified cement pastes. The designated as
glement and the formation of bundles. Characteristics such as the “short” MWCNTs had an average aspect ratio of about 157, whereas
wall number, bulk density, aspect ratio and surface defects induced the “long” MWCNTs had an average aspect ratio of 1250e3750.
by methods of functionalization, also play a crucial role in their Improvement in the flexural strength and ductility was observed
dispersion, hence affecting their reinforcing efficiency and elec- for all 28d specimens. Pastes reinforced with low concentrations of
trical properties [8,12e15]. long MWCNTs exhibited comparable mechanical performance to
Some experiments have been conducted on the effect of the the ones reinforced with higher concentration of short MWCNTs. It
MWCNT geometrical and physical characteristics on the properties was also noticed that for the same concentration the long MWCNT
of MWCNT reinforced pastes and mortars. However, scattered data nanocomposites showed higher strength and less ductility than the
has been reported in literature. Musso et al. [16] studied the way corresponding short MWCNT nanocomposites, probably due to
the chemical and physical properties of the MWCNTs can affect the breakage of the long nanotubes during the sonication process that
mechanical behavior of mortars. The authors fabricated cement in turn leads to a relatively better dispersion of the MWCNTs. More
mortar specimens reinforced with pristine MWCNTs, annealed recently, Stynoski et al. [22] used dispersed pristine carbon nano-
MWCNTs, and carboxyl-group functionalized MWCNTs, at an tubes and silica-functionalized carbon nanotubes at an amount of
amount of 0.5 wt% of cement. Their diameter was in the range of 0.125 wt% in cement mortars. Both types of MWCNTs had the same
40e80 and 10e20 nm and the length between 400 nm and 10 mm. length and diameter. Their results showed that the use of silica
All MWCNTs were dispersed in acetone by means of an ultrasonic functional groups increased the fracture toughness of the MWCNT
probe. The sonication was stopped after 4 h and the acetone was mortars, indicating a stronger frictional bond between the matrix
allowed to evaporate. The authors concluded that the mechanical and reinforcement. A stronger elastic bond was also shown by an
strength of cement composite was strongly affected by the defects increase in the nanocomposite elastic modulus when silica func-
and chemical properties of the MWCNTs utilized: the flexural and tional groups are used with MWCNTs.
the compressive strengths of cement composite reinforced with Whilst the aforementioned studies so far concentrate in exper-
carboxyl-group functionalized CNTs exhibited a significant reduc- imentally determining either the effect of the aspect ratio of
tion of about 158% when compared to plain cement mortar. Pristine MWCNTs or their chemical functionalization in the mechanical
and annealed MWCNTs however, resulted to an improvement in properties of nanoreinforced cement pastes and mortars, there is
the flexural strength of 35 and 10% and in the compressive strength practically no information available in the literature about the ef-
of 11 and 17%, respectively. Konsta-Gdoutos et al. [5,8,17,18] studied fect of the bulk density of MWCNTs on the mechanical properties of
the effects of small amounts (0.048 wt% and 0.08 wt% of cement) of the cement-based nanocomposites. Results from the literature
different aspect ratio MWCNTs on the fracture and nanoscale suggest that reinforcing at the nanoscale with low bulk density
properties, and microstructure of nanoreinforced cement pastes. MWCNTs results in a more efficient and uniform dispersion in most
Two different types of MWCNTs, designated as “short” and “long”, types of matrices. In polymeric matrices, the successful incorpo-
were used with an aspect ratio and surface area of 700 and 1600 ration of low bulk density MWCNTs can lead to polymer nano-
and 110e250/300, respectively. Results from fracture mechanics composites exhibiting superior properties. The effect of the
tests indicated that the fracture properties of the cementitious MWCNTs's bulk density on the mechanical properties of high
matrix greatly improved in all cases. Higher concentrations of short density polyethylene nanocomposites was reported by Morcom
MWCNTs are required to achieve effective reinforcement, while et al. [23]. The authors used 5 different types of MWCNTs including
lower amounts of longer MWCNTs are needed to achieve the same thin, purified and COOH-functionalized MWCNTs with different
degree of mechanical performance. Nanoindentation results sug- bulk densities. Experimental results from tensile tests, conducted
gested that MWCNTs can strongly reinforce the cement paste ma- on dog-bone polyethylene nanocomposites, indicated that the
trix at the nanoscale by increasing the amount of high stiffness lower bulk density of MWCNTs would allow an easier path for the
CeSeH and decreasing the porosity. Sobolkina et al. [19] investi- polymer to infiltrate between the nanotubes and would also
gated the effect of two types of MWCNTs, with their lengths being improve the ability of these materials to be dispersed. The lower
different by one order of magnitude. The first type of MWCNTs the bulk density of MWCNTs the higher the mechanical properties,
measured approximately 20 mm in length at a diameter of with the polymer reinforced with the lower bulk density MWCNTs
approximately 1e15 nm; the length of second type typically exhibiting the higher improvement in both Young's modulus (66%)
measured 100e300 mm with a diameter of approximately and yield stress (69%).
15e40 nm. Dispersion of the 0.5 wt% MWCNT suspensions was Aside from the superior mechanical properties, the electrome-
accomplished in water containing a surfactant and using a soni- chanical characteristics of MWCNTs open new potential applica-
cator operated at an amplitude of 70% for 30, 150, and 210 min. The tions for cementitious nanocomposites with added multi-
authors conducted uniaxial quasi static and dynamic compression functionality. Results of experimental studies on MWCNT rein-
and tensile tests. The modification of the cement pastes with the forced cementitious materials converge to the point that the
dispersed MWCNTs led to an increase of up to 40% in compressive addition of carbon nanotubes improve the electrical properties of
strength and to a less than 10% increase in tensile strength under the nanocomposite material by reducing its resistivity and
 M.S. Konsta-Gdoutos et al. / Cement and Concrete Composites 82 (2017) 137e151 139

providing self sensing properties, under the condition that an using four different types of well dispersed pristine and function-
effective degree of the nanotubes' dispersion has been achieved alized MWCNTs at an amount of 0.1 wt% of cement took place
[24e27]. Saafi et al. [24] investigated the resistivity of cementitious through: (i) flow and time of setting tests; (ii) three point bending
nanocomposites reinforced with MWCNTs. The electrical resistance experiments on 4  4  16 cm specimens; and (iii) uniaxial
decreased as the volume of MWCNTs increased from 0 to 1.0 wt%. A compression on the half prisms of the flexural test specimens
slight decrease was observed when the volume of MWCNTs was (4  4  8 cm). The strain sensing ability expressed as the fractional
increased beyond 1.0 wt%. Konsta-Gdoutos and Aza [25] deter- change in resistivity of the mortars reinforced with the pristine
mined the electrical resistance and piezoresistivity of cement MWCNTs was experimentally determined using the 4-pole method
pastes with w/c ¼ 0.3, reinforced with well dispersed MWCNTs at under a cyclic compressive load, and compared with the piezor-
amounts of 0.1 and 0.3 wt%. DC resistivity measurements per- esistive behavior of the mortars reinforced with the functionalized
formed at 28d pastes showed a decrease in electrical resistance, MWCNTs.
with the nanocomposites containing 0.1 wt% MWCNTs exhibiting
the lower resistivity value. The authors also compared the piezor- 2. Experimental work
esistive behavior of 0.1 and 0.3 wt% MWCNT and CNF reinforced
cement pastes and concluded that the 0.1 wt% of both MWCNT and 2.1. Materials, mixture preparation and specimens
CNF mixes presented a higher fractional change in resistivity.
Azhari and Banthia [26] investigated the ability of conductive Type I ordinary Portland cement (OPC) 42.5 R and standard sand
cementitious composites, carrying carbon fibers (CFs) and CNTs, to according to EN 196-1 were used for casting the mortar specimens.
sense applied compressive load through a measureable change in Four different types of MWCNTs were used to reinforce the
resistivity. The cementitious composite materials reinforced with cementitious mortars. Types 1000C1 and 1000C2 are designated as
either CFs or CNTs respond well to an applied compressive strain by “pristine MWCNTs”. They have similar bulk density, and different
depicting a reduction in its resistivity, and this applies to both aspect ratio and specific surface: (i) the length of type 1000C2 is
monotonically and cyclically applied strain fields. More recently, considerably smaller and so is the diameter; and (ii) the specific
Han et al. [27] investigated the piezoresistive behavior of smart surface of 1000C2 is 1.5 times higher (150 m2/g) than this of 1000C1
cement-based mortars reinforced with electrostatic self-assembled (100 m2/g). Both types of the pristine MWCNTs (1000C1 and
CNT/nano carbon black (NCB) composite fillers. The resistance was 1000C2) were produced in a fluidized bed chemical vapor deposi-
measured by DC two electrode method. The authors concluded that tion reactor, employing proprietary methodologies and metal cat-
the optimal content level of CNT/NCB composite fillers is 2.40 vol% alysts as well as ethylene as carbon source [30]. Type 1000C3
for piezoresistivity. The fractional change of electrical resistivity of resulted by a mechanical functionalization of the pristine1000C1
cement mortars with 2.40 vol% CNT/NCB composite fillers under MWCNTs, applied by the manufacturer. As it is depicted from
compressive loading was 22.1%. Table 1, types 1000C1 and 1000C3 have the same length, almost the
Development of multi-functional nanocomposites usually re- same diameter, however type 1000C3 exhibits a significantly lower
quires functionalization of MWCNTs to allow a better interfacial bulk density. The fourth type, MWCNTs 1001F was obtained by
bonding with the matrix. However, depending on the procedure of chemically functionalizing pristine MWCNTs. According to the
this chemical or mechanical modification a different effect on the manufacturer's specifications, pristine MWCNTs were ultra-
intrinsic properties of MWCNTs may be observed. Li et al. [28] used sonicated in a nitric acid solution (HNO3) for 10 min at a CNTs/HNO3
MWCNTs treated with a mixed solution of H2SO4 and HNO3 weight ratio of 1/30. Subsequently, the mixture was mechanically
(SPCNT) and pristine MWCNTs (PCNT) to reinforce cement pastes. stirred in oil bath at 100  C for 48 h. Carbon nanotubes were then
They reported that both pristine and functionalized MWCNTs retrieved through filtering until their pH reached the value of 7.
greatly reduced the electrical resistance of the cementitious matrix, Finally, the CNTs were dried in a vacuum oven overnight at 70  C.
with the 28d nanocomposites reinforced by the pristine MWCNTs From the aforementioned process carboxylic groups COOH were
to exhibit higher conductivity. More recently, McClory et al. [29] produced that provide the functionalized MWCNTs with the ability
investigated the electrical percolation of poly methyl methacry- of a uniform and effective dispersion, without the need of a soni-
late (PMMA) nanocomposites reinforced with pristine and car- cation procedure.
boxylic acid MWCNTs. The DC resistivity measurements on PMMA The properties of the MWCNTs used in this study are shown in
nanocomposites indicated that no electrically conducting perco- Table 1. Values of an estimated fiber count, the number of fibers (in
lated network was obtained with the incorporation of chemical this case MWCNTs), which are theoretically evenly distributed in a
functionalized MWCNTs in the polymer matrix. The authors unit volume of the matrix, assuming perfect dispersion according
concluded that the carboxylic acid functional groups disturbed the to ACI 544.1R-96: Report on Fiber Reinforced Concrete [31], is
graphitic structure of the nanotube and destroyed the electron determined from the relationship:
hopping and tunneling of the MWCNTs' network. As a result, the
" #
chemical functionalized MWCNTs did not alter the resistivity of the 0:0127ðVÞ
polymer matrix. FC ¼   (1)
In this work, we present a comprehensive analysis on the effect
L d2
of the aspect ratio, bulk density and functionalization of commer-
cially available MWCNTs in the development of Portland cement
nanomodified mortars. A simple, one step dispersion method,
involving the application of ultrasonic energy and the use of a Table 1
Properties of multiwall carbon nanotubes (MWCNTs).
superplasticizer (SP), was utilized for the preparation of the
MWCNTs aqueous suspensions. A structural characterization of the Type Diameter, Length, Surface area, Bulk density, Aspect Ratio
pristine and functionalized carbon nanotubes was carried out with nm mm m2/gr gr/cm3
scanning electron microscopy (SEM), transmission electron mi- 1000C1 20e45 10 >100 0.18 307
croscopy (TEM), and thermogravimetric analysis (TGA). The 1000C2 15e35 5 >150 0.17 200
experimental determination of the fresh and mechanical properties 1000C3 20e40 10 >150 0.07 333
1001F 20e40 10 >150 0.07 333
of nanomodified cement mortars with w/c ¼ 0.5 and s/c ¼ 3.0,
140 M.S. Konsta-Gdoutos et al. / Cement and Concrete Composites 82 (2017) 137e151

where V is the fiber content, percent by volume, L is the length of an 2.2. Testing procedure
individual MWCNTs and d is the equivalent fiber diameter.
Generally, for any given volume percentage of fibers of equal 2.2.1. Properties of fresh mortars
length that can ideally be assumed uniformly distributed in a ma- Flow tests were performed in compliance with ASTM C 1437 to
terial mix, the number of individual fibers per unit volume varies investigate the effect of incorporation of MWCNTs on the work-
inversely with the square of the individual fiber diameter and can ability of cement mortars. The experimental setup is shown in
be calculated by using the following equation: Fig. 1a. The cone was filled and compacted according to ASTM C
1437. The table was dropped at a rate adequate to achieve 25 drops
in approximately 15 s. The diameter of the mortar was then
measured along the four lines scribed in the table top, as shown in
VIF Fig. 1a. The flow values were calculated according to the equation:
FC ¼ (2)
Vf
Dm  Dc
where the VIF is the volume of an individual fiber and Vf is the F¼  100% (4)
Dc
volume fraction of the fiber per unit volume, which can easily
calculated by the equation: where Dm is the average fresh mortar diameter and DC is the
diameter of the cone.
The time at which the needle penetrates 25 mm into the mortar
mixtures at room temperature was taken to define the initial
Mf
Vf ¼ (3) setting using an automatic Vicat apparatus and following ASTM 191
rB (Fig. 1b).

where Mf is the fiber content, percent by mass and rB is the bulk

density of the fibers. 2.2.2. Mechanical properties
From the aforementioned determination of the MWCNT count Three point bending tests were conducted to assess the flexural
per unit volume, it is clearly observed that the MWCNT count de- performance of the nanoreinforced mortars. 4  4  16 cm pris-
pends on the bulk density: the lower the bulk density the higher matic specimens were prepared using the mixing protocol
the fiber count. The calculated MWCNT count for all mortar mixes is described previously, and tested in three-point bending at the age
presented in Table 2. The dispersion of MWCNTs is a challenging of 3, 7 and 28 days. The test was performed using a 25 kN MTS
procedure, primarily due to the strong interaction forces that cause servo-hydraulic, closed-loop testing machine under displacement
the entanglement and the formation of bundles in the pristine control. The rate of displacement was kept as 0.1 mm/min. The
MWCNTs. In this work, a simple, one step dispersion method flexural toughness T is the energy required for the material to fail
[32,33] was followed to achieve homogeneous dispersion of and was determined by integrating the 3 point bending load-
MWCNTs in the cementitious mixture. In a typical dispersion pro- deflection curve of the nanoreinforced mortars.
cedure the MWCNT/suspensions are prepared by adding MWCNTs The compressive strength of the mortar nanocomposites was
to an aqueous polycarboxylate based surfactant solution, at a sur- determined on the halves of the prisms after the fracture of the
factant to nanotube weight ratio of 4.0. Ultrasonic energy is applied flexure specimens, according to ASTM C349 and ASTM C109. Prior
to the suspensions by a 500 W cup-horn high intensity ultrasonic to subjecting them to the uniaxial compression test, the two halves
processor with a standard probe of a diameter of 19 mm and a were examined for the presence of cracks that might have been
temperature controller. The sonicator is operated at amplitude of generated during the three point bending test. The test was per-
57% so as to deliver constant energy rate of 1900e2100 J/min, at formed using a 250 kN MTS servo-hydraulic, closed-loop testing
cycles of 20 s in order to prevent overheating of the suspensions. machine under displacement control. The rate of displacement was
The MWCNT/suspensions were then added into the OPC, sand at a kept as 0.3 mm/s.
constant water to cement ratio w/c ¼ 0.5, and sand to cement ratio According to ASTM C348 and ASTM C349 the specimens that
s/c ¼ 3.0. Mixing of the materials was performed according to the result in strengths differing by more than 10% from the average
procedure outlined by ASTM 305 using a standard robust mixer value of all test specimens made from the same sample and tested
capable of operating from 140 ± 5 revolutions per minute (r/min) to
285 ± 10 r/min. After mixing, one set of the mixture was cast in
4  4  16 cm oiled molds for the mechanical testing and another
set in 2  2  8 cm oiled molds for the resistivity testing. Following
demolding, the samples were cured in lime-saturated water until
testing. For the piezoresistivity measurements metallic grids with
large opening (3  3mm) were embedded into the specimens
immediately after casting. The piezoresistivity specimens were
allowed to oven-dry for three days at 95  C before testing in order
to eliminate the effect of polarization.

Table 2
List of specimens and MWCNT count.

MWCNT count

M e
Mþ1000C1 0.1 wt% 3.6  1011
Mþ1000C2 0.1 wt% 12.9  1011
Mþ1000C3 0.1 wt% 10.9  1011
Mþ1001F 0.1 wt% 10.9  1011
Fig. 1. (a) flow test apparatus and (b) vicat apparatus for the testing time set.
 M.S. Konsta-Gdoutos et al. / Cement and Concrete Composites 82 (2017) 137e151 141

at the same period were not considered in determining both flex- 1000C1 grade and 20e40 nm for 1000C3 grade, as confirmed by the
ural strength and compressive strength. Following the above TEM microscopy images shown in Fig. 3. The micrographs were
mentioned procedure assures that the variations of the test results obtained in a Hitachi H7650 microscope.
are not significant and do not affect the conclusions. Using Thermogravimetric Analysis (TGA) in air, the carbon
content of pristine MWCNTs was determined to be around 98.1% for
2.2.3. Strain sensing-Piezoresistivity experiments 1000C1 (i.e. metal catalysts particle content ¼ 1.9%) and 94.6% for
The piezoresistive behavior of 28 day mortar nanocomposites 1000C3 (Figs. 4 and 5, respectively), with the amount of amorphous
was investigated using the four pole method while cyclic uniaxial carbon in the carbon content being minimal for both cases. The
compressive loading was simultaneously applied to the specimens combustion of MWCNTs takes place at temperatures above 550  C,
from a hydraulic testing machine MTS with a 25 kN capacity. The whereas that of amorphous carbon at 300e350  C. The TGA anal-
electrical resistance of the mortar nanocomposites was measured ysis of functionalized MWCNTs in inert atmosphere (Fig. 6)
using two digital multimeters (Fluke 289 AC/DC True RMS) with the revealed a 5.5% wt% percentage of carboxyl groups in the 1001F
ability to measure mA and V, and a power supply unit (Mastech sample. A Perkin Elmer TGA 4000 was employed for the analysis.
HY3005D) capable of supplying direct current (DC) up to 30 V. The
multimeter connected with the inner electrodes was used to
measure the voltage difference, while the one connected with the 3.2. Fresh properties of MWCNT reinforced mortars
outer electrodes and the power supply unit was used for the cur-
rent intensity measurements. To take into account the nature and Mortar flow is a relative measure of workability. Fig. 7 presents
geometry of the nanocomposites, the resistance measurements the visual observation of the flow test of the plain mortar and the
were converted to electrical resistivity (r) calculated as resistance 0.1 wt% 1000C1, 1000C2 and 1000C3 MWCNTs mortar nano-
per unit length: composites. As it can be seen from Fig. 7 and Table 3, the flow
spread of the MWCNT reinforced mortars decreased with the
RS MWCNT fiber count: the 1000C2 mortar mixture, which exhibits
r¼ (5)
the highest fiber count (12.9$1011) of individual MWCNTs assuming
L
perfect dispersion, exhibits the lowest flow spread (86%), followed
where, R is the resistance of the nanocomposite, S the cross-section by the 1000C3 mortar (91%), and the 1000C1 mortar (102%), which
area of the specimen and L the distance between the two inner exhibits the lowest MWCNT count (3.6  1011). We should note at
electrodes. The cyclic compressive loading of maximum 2 kN this point that all these mixes contain superplasticizer (SP) to
(approximately 5 MPa) was applied to each specimen. Every promote stable dispersion through adsorption and surface accu-
loading-unloading cycle had duration of approximately 120 s. The mulation on the nanotubes' surface. Despite the fact that the water,
values of load, voltage and current intensity were recorded every SP, cement and sand content is the same in all mortar mixtures,
1 s, with the experimental procedure lasting 600e800s for each higher fiber count mixes consume higher amount of SP, due to a
specimen. higher amount of individual MWCNTs. Therefore, a smaller amount
of SP remains available for interaction with the cement grains and
3. Results and discussions the mix appears to lose its workability.
The initial time of setting corresponds to the beginning of the
3.1. Micro and nano structural characterization of MWCNTs stiffening of the mortar and the loss of workability. When in contact
with water cement starts hydrating. It has long been recognized
Structural characterization of carbon nanotubes was carried out that the use of polycarboxylate SPs may retard cement hydration.
with scanning electron microscopy (SEM), transmission electron As depicted from Fig. 8 the OPC mortar containing 0.4 wt% of
microscopy (TEM), and thermogravimetric analysis (TGA). cement SP exhibits an initial time of setting of 2 h and 50 min. A
Fig. 2 shows representative SEM micrographs of pristine slight acceleration of the time of setting was observed for the
MWCNTs (1000C1 and 1000C3), taken on a Zeiss SUPRA 35VP SEM nanomodified 1000C1, 1000C2 and 1000C3 mortar mixtures when
microscope. In all images, only bundles of multi-wall carbon compared to the plain mortar. Initial setting time for the mixture
nanotubes are observed and there is no sign of any impurities e.g., reinforced with 0.1 wt% 1000C1 MWCNTs was approximately 2 h
amorphous carbon, which would be present in granular form. and 25 min. The pristine 1000C2 nanomodified mortar and the
Especially, as we can see in Fig. 2b, only the existing carbon mechanically functionalized 1000C3 mortar exhibited an initial
nanotubes are illustrated in a typical form of ribbon complexes. setting time of 2 h and 15 min. Assuming that a good amount of SP
The diameter of MWCNTs varies between 20 and 45 nm for is adsorbed on the nanotubes surface, less amount of the SP is

Fig. 2. SEM micrographs of pristine MWCNTs: (a) 1000C1, (b): 1000C3.

142 M.S. Konsta-Gdoutos et al. / Cement and Concrete Composites 82 (2017) 137e151

Fig. 3. TEM images of pristine MWCNTs: (a) 1000C1, (b): 1000C3.

Fig. 4. TGA curve of pristine MWCNTs 1000C1 in air.

available in the mortar matrix to interact with cement, when MWCNTs the smaller diameter and length of the 1000C2 MWCNTs
compared with the neat mortar mix that contains the same amount (Table 1) resulted in a smaller aspect ratio. On this basis, the
of SP. Therefore time of setting occurs a little earlier for all nano- geometrical characteristics (and consequently the aspect ratio)
reinforced mortars [34]. possibly play an important role in the reinforcing efficiency, in spite
of the fact that the count of individual MWCNTs that are theoreti-
3.3. Effect of the MWCNTs' aspect ratio, bulk density and cally uniformly distributed in the mortar matrix is twice as much as
mechanical functionalization on strength, stiffness and energy the 1000C1 (Table 2). The highest improvement in the flexural
absorption ability of MWCNT reinforced mortars strength was seen in the mechanically functionalized 1000C3
MWCNTs specimens. This type of MWCNTs resulted by a manu-
Results of the three point bending tests of the flexural strength, facturer's mechanical functionalization of Type 1000C1 pristine
sf, of mortars reinforced with the two different types of pristine MWCNTs. As it is depicted from Table 1 types 1000C1 and 1000C3
MWCNTs (1000C1 and 1000C2) and the mechanically functional- have the same length, almost the same diameter, however type
ized MWCNTs (1000C3) at an amount of 0.1 wt% of cement are 1000C3 MWCNTs have remarkably lower bulk density. As discussed
presented in Fig. 9. This particular amount of MWCNTs was found above, geometrical parameters such as length and diameter, as well
from previous studies to produce mortar nanocomposites with as bulk density are used to calculate the fiber count of individual
notably high mechanical and fracture properties [7,35,36]. All fibers in a unit volume of cementitious matrix [31]. It is observed
MWCNT reinforced mortars exhibit higher flexural strength than from Table 2 that the count of well dispersed 1000C3 MWCNTs at
the plain mortar at all 3 ages. The mortars reinforced with the two the amount of 0.1 wt% is approximately three times higher than the
pristine MWCNTs, 1000C1 and 1000C2 exhibit a 78%, and 73% in- count of 1000C1 MWCNTs (when dispersed at the same amount,
crease in flexural strength respectively. Compared to the 1000C1 following the same dispersion conditions and sonication
 M.S. Konsta-Gdoutos et al. / Cement and Concrete Composites 82 (2017) 137e151 143

Fig. 5. TGA curves of 1000C3 MWCNTs in air.

Fig. 6. TGA curve of 1001F (COOH-CNTs) in inert atmosphere.

procedure). incorporation. The 28d of the 0.1 wt% 1000C1 and 1000C2 MWCNT
The Young's modulus results of plain mortar and 0.1 wt% nanoreinforced mortars exhibit a 87% and 84% increase in Young's
1000C1, 1000C2 and 1000C3 MWCNT reinforced mortars are pre- modulus respectively. Type 1000C3 MWCNT nanocomposite yields
sented in Fig. 10. Similarly to the flexural strength results, the the extraordinary increase of 124%. By comparison, it is obvious
Young's modulus impressively increases with the MWCNTs that the mechanical functionalization of the pristine 1000C1
144 M.S. Konsta-Gdoutos et al. / Cement and Concrete Composites 82 (2017) 137e151

reinforced with 1000C1, 1000C2 and 1000C3 MWCNTs at an

amount of 0.1 wt% of cement after 28 days of hydration is depicted
in Fig. 11. Interestingly, only a modest improvement of the
compressive strength was observed. The 28d 1000C1, 1000C2 and
1000C3 MWCNT nanoreinforced mortars exhibit a 5%, 4% and 6%
increase in compressive strength, respectively. The results indicate
that in contrast to the flexural strength (Fig. 9) and Young's
modulus results (Fig. 10), MWCNTs have only a marginal effect on
the compressive strength. The compressive and tensile Young's
modulus of the 28d aforementioned samples was calculated from
both the uniaxial compression and three point bending tests, and is
presented in Fig. 12. It is observed that all mortar nanocomposites
reinforced with MWCNTs exhibit almost 100% higher Young's
modulus over the plain one. The impressive increase in Young's
modulus of about 124% observed for the 28d 1000C3 MWCNT
nanomodified mortar can be attributed to the beneficial effects of
the mechanical functionalization that resulted in a strengthened
mortar/CNT interface. It should be noted here that the compressive
stiffness values perfectly agree with the values calculated by the
stress-strain curves from the three-point bending tests.
The flexural toughness of cement-based material is the amount
of energy per unit volume that the material can absorb until failure.
In general, the energy absorption capability of a cementitious ma-
terial is the energy of mechanical deformation per unit volume
prior to fracture and can be determined by integrating a 3 point
bending load-deflection curve. The load-deflection curves of 28d
Fig. 7. Flow test results of (a) plain mortar and mortar mixes reinforced with (b)
1000C1 (c) 1000C2 and (d) 1000C3 MWCNTs at an amount of 0.1 wt% of cement. plain mortar and 0.1 wt% 1000C1, 1000C2 and 1000C3 nano-
composites are presented in Fig. 13. As depicted from Fig. 13,
toughness is essentially the product of applied stress and me-
chanical deformation. Similarly to the flexural strength and stiff-
Table 3 ness results, the incorporation of well dispersed MWCNTs results in
Flow ability of plain mortar and mortar mixes nanomodified by different types of a higher load requirement for the same mechanical deformation for
MWCNTs at amount of 0.1 wt% of cement. all samples. As shown in Fig. 14, the 28d nanocomposites reinforced
SP (wt%) MWCNTs count Flow (%) with 1000C1, 1000C2 and 1000C3 MWCNTs at amount of 0.1 wt%
exhibit an increase in the flexural toughness of 82%, 71%, and 103%
M 0.4 e 121
Mþ1000C1 0.4 3.6  1011 102 respectively. This significant improvement of the flexural tough-
Mþ1000C2 0.4 12.9  1011 86 ness (or energy absorption capacity) of the nanoenhanced mortars
Mþ1000C3 0.4 10.9  1011 91 is attributed to a more controlled crack coalescence process at the
nano and microscale. This increased energy absorption capability
suggests that a significant amount of energy is required for the
resulted in a material (1000C3) that can greatly attain a good material to fail and for the cracks to propagate. This can be also seen
adhesion with the mortar matrix, manifested in extraordinary in- from Fig. 15, where both the crack width and length that corre-
creases in strength and stiffness. spond to the fracture load of the nanoreinforced mortars are
The compressive strength, sc, of the plain mortar and mortars reduced.

Fig. 8. Setting time of plain mortar and mortars reinforced with pristine and functionalized MWCNTs at an amount of 0.1 wt% of cement.
 M.S. Konsta-Gdoutos et al. / Cement and Concrete Composites 82 (2017) 137e151 145

Fig. 9. Effect of MWCNT type on the flexural strength, sf, of mortar nanocomposites reinforced with 0.1 wt% MWCNTs at the age of 3, 7 and 28 days.

Fig. 10. Young's modulus, E, of mortars reinforced with different types of MWCNTs at an amount of 0.1 wt% at the age of 3, 7 and 28 days.

Fig. 11. 28d compressive strength, sc, of mortars reinforced with different types of MWCNTs at an amount of 0.1 wt%. of cement.

3.4. Chemically functionalized MWCNTs analysis two nanoreinforced mortars were prepared and tested: (a)
mortars reinforced with effectively “dispersed” 1001F MWCNTs;
3.4.1. Effect of MWCNT chemical functionalization on the fresh and (b) mortars reinforced with “as received” 1001F MWCNTs.
properties of mortars Fig. 16 shows pictures of suspensions prepared with 0.1 wt%
Chemical functionalization is usually used to tailor and enhance 1001F MWCNTs “as received” and after the sonication procedure.
the interaction of the nanotubes with the matrix. As mentioned Many agglomerates can be seen on the “as received” 1001F sus-
previously, type 1001F MWCNTs were developed by chemically pension container's walls. The flow spread of “dispersed” and “as
functionalizing pristine MWCNTs, so that the outer surface of the received” 0.1 wt% 1001F MWCNT reinforced mortars is presented in
nanotubes is modified by carboxylic groups COOH. This chemical Fig. 17. As it can be seen from Fig. 17 and Table 4, a lower workability
functionalization provides the MWCNTs with the ability to uni- (92%) of the mortar mixture containing the “dispersed” chemically
formly disperse in a material, and without the need of any soni- functionalized MWCNTs was observed over the “as received”
cation procedure or additional dispersion means. In the following MWCNTs. During ultrasonication, after the surfactant has been
146 M.S. Konsta-Gdoutos et al. / Cement and Concrete Composites 82 (2017) 137e151

Fig. 12. Effect of MWCNT type on the compressive and tensile Young's modulus of MWCNT reinforced mortars.

Fig. 13. Load-Deflection curves of 28d plain mortar and mortars reinforced with different types of MWCNTs at an amount of 0.1 wt% of cement.

Fig. 14. Effect of MWCNT type on the flexural toughness of mortar nanocomposites (w/c/s ¼ 0.5/1.0/3.0) reinforced with 0.1 wt% MWCNTs at the age of 28 days.

adsorbed on the nanotube's surface, the tremendous energy sup- they potentially adsorb a higher amount of SP on their surface;
plied by the sonication helps the surfactant to further detangle the hence less amount of SP is available for the dispersion of cement in
nanotubes by steric or electrostatic repulsions [37]. Therefore, the the mortar matrix, which slightly affects the workability.
amount of individual MWCNTs in the “dispersed” suspension is The time of initial setting for plain mortar and mortar reinforced
definitely higher than in the “as received” mix due to the applica- the chemical functionalized 0.1 wt% 1001F MWCNTs as received
tion of sonication energy. The flow behavior of the pastes and and after the dispersion method is shown in Fig. 18. The sonication
mortars is mainly controlled by the dispersion of cement. When a procedure that the “dispersed” 1001F MWCNTs underwent helped
higher number of well dispersed MWCNTs is present in the mix the SP to get adsorbed on the nanotubes surface. As a result less
 M.S. Konsta-Gdoutos et al. / Cement and Concrete Composites 82 (2017) 137e151 147

Fig. 15. Failure patterns of 28d (a) plain mortar and (b) 0.1 wt% 1000C3 MWCNT nanomodified mortar.

Table 4
Flow ability of plain mortar and mortars reinforced with 1001F (“dispersed” and “as
received”) MWCNTs at an amount of 0.1 wt% of cement.

SP (wt%) MWCNTs count Flow (%)

M 0.4 e 121
Mþ1001F “dispersed” 0.4 10.9  1011 92
Mþ1001F “as received” 0.4 10.9  1011 109

amount of SP is available in the mortar mix, therefore the

“dispersed” 1001F MWCNT mortar mix exhibits a slight accelera-
tion of 20 min in its initial setting time over to the plain mortar, and
10 min over the “as received” nanoreinforced mortar.

3.4.2. Effect of MWCNT chemical functionalization on the

mechanical properties of the nanoreinforced mortars
Fig. 19 presents the rate of the flexural strength development of
the mortar nanocomposites reinforced with the 1000C3 and 1001F
“dispersed” and “as received” MWCNTs, at an amount of 0.1 wt% of
cement. The values of the properties of type 1000C3 were also
Fig. 16. Aqueous suspension containing the chemical functionalized 1001F MWCNTs included for comparison, as all three mortar mixes have the same
(a) “as received” and (b) “dispersed”. nanotube count. Compared to the neat mortar, all nanomodified
mortars exhibit higher flexural strength: the 1000C3 MWCNT
mortar exhibited a 119% increase, while the “dispersed” 1001F, and
the “as received” 1001F MWCNT reinforced mortars exhibited an
80% and 51% increase in flexural strength respectively. It is inter-
esting to note here that chemical functionalization resulted in the
presence of modified carboxyl groups, which in turn lead to a
reduction of the van der Waals forces between the MWCNTs. As a
result the “as received” 1001F MWCNTs were already in the form of
individual tubes that could easily be used in water and did not
require any additional form of dispersion such as sonication. Yet,
the “dispersed” 1001F MWCNTs were able to more effectively
reinforce the mortar matrix than the “as received” 1001F, probably
because this chemical functionalization treatment without the
means of ultrasonication did not render the MWCNTs the same
degree of dispersion. As it is shown from Fig. 16 many agglomerates
can be seen on the “as received” 0.1 wt% 1001F MWCNT suspension
Fig. 17. Flow test results of mortar mixes reinforced with (a) “dispersed” and (b) “as container's walls. These inclusions act as stress concentration areas,
received” 1001F MWCNTs at an amount of 0.1 wt% of cement. leading to a degrade of both the mechanical and fracture properties
148 M.S. Konsta-Gdoutos et al. / Cement and Concrete Composites 82 (2017) 137e151

Fig. 18. Setting time of mortars reinforced with 0.1 wt% of cement “dispersed” and “as received” 1001F MWCNTs.

Fig. 19. Rate of flexural strength, development, sf, of mortars reinforced with mechanically functionalized 1000C3 MWCNTs, and as received and well dispersed 1001F MWCNTs.

of the nanoreinforced mortars [35]. 3.5. Effect of fiber count and functionalization of MWCNTs on
From the results presented in Fig. 19 it is also observed that strain-sensing
although types 1000C3 and 1001F MWCNTs present the same
nanotube count, both the “as received” and “dispersed” 1001F Piezoresistivity measurements were carried out to study the
MWCNT reinforced mortars consistently exhibited lower flexural effect of the fiber count and functionalization on the change of the
strength than the 1000C3 mortars. It is possible that the polar mortars' electrical properties and its ability to realize the change in
functional groups such as eOH, eCeO, attached to the surface of strain. The fractional change in resistivity was found to provide a
the 1001F MWCNTs, could lead to a slight decrease of the MWCNTs/ much more valuable indication of the change of the electrical
mortar interfacial interaction [38]. properties and the effect of functionalization. Results are presented
The Young's modulus results of the 0.1 wt% “dispersed” and “as in Fig. 21. The addition of pristine 1000C1 MWCNTs was found to
received” 1001F and 1000C3 MWCNT 28d mortars are presented in have a great influence on the piezoresistive response as the 0.1 wt%
Fig. 20. In general, Young's modulus follows the same trend as 1000C1 MWCNT reinforced mortar yielded a fractional change in
flexural strength: The modulus of both the mechanically and resistivity, of about 10.6%. The addition of the mechanically modi-
chemically functionalized MWCNT reinforced mortars is impres- fied 1000C3 MWCNTs and chemically modified “dispersed” and as
sively increased. However, despite the same MWCNT count, both received 1001F MWCNTs however did not result in any piezor-
the “as received” and “dispersed” 1001F MWCNTs mortars exhibit a esistive response, despite the good dispersion, the higher aspect
lower increase compared to the 1000C3 reinforced mortars. It is ratio, the larger surface area and the higher count of individual
possible that the strong acid treatment can significantly disrupt the MWCNTs in the mortar matrix (Table 2). Mechanical and chemical
MWCNT structure which can result in a reduction of the MWCNTs' functionalization introduces structural defects and disrupts the
length during mechanical deformations [39]. It has been previously single and multiple bonds of electrons, in chemistry called as p-
reported that when MWCNTs are oxidized by a mixture of sulfuric conjugation system, in surface of carbon nanotubes; hence func-
and nitric acids, their length can dramatically decrease [40]. As a tionalized MWCNTs do not always retain the electrical properties of
result, the interfacial length between the nanotubes and the matrix pristine MWCNTs [35,42,43]. Cho et al. [44] concluded that the
becomes smaller. The weaker interfacial bonding can decrease the electrical conductivity of the surface-functionalized MWCNT
stress transfer efficiency from the matrix to the nanotubes, when nanocomposites was lower than that of the pristine MWCNT-
loading is applied in the nanocomposite specimens [41]. nanocomposites that had the same MWCNT content in the ma-
trix. This is attributed to increased defects in the lattice structure of
 M.S. Konsta-Gdoutos et al. / Cement and Concrete Composites 82 (2017) 137e151 149

Fig. 20. Young's modulus of 28d mortars reinforced with mechanically functionalized 1000C3, “as received” and “dispersed” chemically functionalized 1001F MWCNTs.

Fig. 21. Piezoresistivity behavior of 28d mortars reinforced with 1000C1, 1000C3, “dispersed” and “as received” 1001F MWCNTs at an amount of 0.1 wt%.

carbon-carbon bonds on the nanotube surface as a result of the acid occurs a little earlier for all nanoreinforced mortars and at the same
treatment. As a result, both the chemical and mechanical modifi- time they exhibit a slight workability loss. The workability and time
cation resulted in nanotubes with inferior electric properties, hence of setting of the chemically functionalized CNTs follow the same
with diminished piezoresistive and self sensing ability. trend.
All MWCNT reinforced mortars exhibit much higher flexural
strength, Young's modulus and energy absorption capability than
4. Conclusions
the plain mortar at all ages. It was found that the lower the bulk
density of MWCNTs the more enhanced the mechanical properties
To unlock the carbon nanotubes' contribution in structural ap-
are. The highest improvement in the mechanical properties was
plications it is necessary to take into account the differences in their
seen in the mechanically functionalized 1000C3 MWCNTs speci-
geometrical and physical characteristics and structure. This work
mens. These nanotubes are characterized by a high count,
focused on the effect of aspect ratio, bulk density and functionali-
approximately three times higher than the count of 1000C1
zation of multi walled carbon nanotubes (MWCNTs) in the devel-
MWCNTs, and the lowest bulk density. The impressive increase of
opment of nanomodified mortars. It is demonstrated that the
118% in flexural strength, 124% in Young's modulus and 103% in
MWCNT count depends on the bulk density: the lower the bulk
flexural toughness that the 1000C3 MWCNT nanomodified mortars
density the higher the fiber count. Fresh properties, namely flow
presented can be attributed to the beneficial effects of the me-
ability and setting time of the pristine MWCNTs and mechanically
chanical functionalization that resulted in a lower bulk density and
functionalized MWCNTs exhibit a dependency on the fiber count:
a good adhesion with the mortar matrix that results in strength-
flow spread of the MWCNT reinforced mortars decreased with the
ened mortar/CNT interface.
MWCNT fiber count, while setting time was found to be slightly
Depending on the procedure of the functionalization, chemical
accelerated. Assuming that a good amount of SP is adsorbed on the
or mechanical, a different effect on the intrinsic properties of
nanotubes’ surface, less amount of the SP is available in the mortar
MWCNTs was observed. Compared to the neat mortar, the chemi-
matrix to interact with cement, when compared with the mortar
cally nanomodified mortars exhibit higher flexural strength and
mix that contains the same amount of SP. Therefore time of setting
150 M.S. Konsta-Gdoutos et al. / Cement and Concrete Composites 82 (2017) 137e151

stiffness: the “dispersed” 1001F MWCNT mortar exhibited a 80% (20) (2000) 2868e2870.
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