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
Carbon nanotubes (CNTs) exhibit outstanding mechanical
properties such as a tensile strength of 65e93 GPa and a stiffness of
about 1 TPa [1]. Their particular graphene electronic structure al-
lows them to exhibit semi-conducting, as well as quasi-metallic
and metallic behavior [2,3]. All these, in combination with their
* Corresponding author.
E-mail address: mkonsta@civil.duth.gr (M.S. Konsta-Gdoutos).
high aspect ratio make them ideal reinforcing materials, offering
outstanding improvement to the mechanical and electrical prop-
erties of cementitious matrices that are being used in structural
applications [4e7].
Earlier results in the literature suggest that multiwall carbon
nanotubes (MWCNTs) fundamentally modify the nanostructure of
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-
teristics, and structure. As extensively reviewed in the literature,

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
graphene sheets, coaxially arranged around a central hollow core.
MWCNTs have a high aspect ratio, low bulk density and an
extended specific area, which is of particular interest for adsorption
and reactions taking place on the nanotubes' surface [9,10]. The
interface length and strength depend directly on the geometrical
characteristics of the nanotubes, hence a higher aspect ratio is
required for an effective transfer load between from the matrix to
the nanotube [11]. Another important parameter affecting the
properties of the MWCNT reinforced cementitious materials is the
dispersion of MWCNTs, which has proven a challenging and rather
inconsistent procedure, primarily due to their inherent hydropho-
bic nature and the strong van der Waals forces that cause entan-
glement and the formation of bundles. Characteristics such as the
wall number, bulk density, aspect ratio and surface defects induced
by methods of functionalization, also play a crucial role in their
dispersion, hence affecting their reinforcing efficiency and elec-
trical properties [8,12e15].
Some experiments have been conducted on the effect of the
MWCNT geometrical and physical characteristics on the properties
of MWCNT reinforced pastes and mortars. However, scattered data
has been reported in literature. Musso et al. [16] studied the way
the chemical and physical properties of the MWCNTs can affect the
mechanical behavior of mortars. The authors fabricated cement
mortar specimens reinforced with pristine MWCNTs, annealed
MWCNTs, and carboxyl-group functionalized MWCNTs, at an
amount of 0.5 wt% of cement. Their diameter was in the range of
40e80 and 10e20 nm and the length between 400 nm and 10 mm.
All MWCNTs were dispersed in acetone by means of an ultrasonic
probe. The sonication was stopped after 4 h and the acetone was
allowed to evaporate. The authors concluded that the mechanical
strength of cement composite was strongly affected by the defects
and chemical properties of the MWCNTs utilized: the flexural and
the compressive strengths of cement composite reinforced with
carboxyl-group functionalized CNTs exhibited a significant reduc-
tion of about 158% when compared to plain cement mortar. Pristine
and annealed MWCNTs however, resulted to an improvement in
the flexural strength of 35 and 10% and in the compressive strength
of 11 and 17%, respectively. Konsta-Gdoutos et al. [5,8,17,18] studied
the effects of small amounts (0.048 wt% and 0.08 wt% of cement) of
different aspect ratio MWCNTs on the fracture and nanoscale
properties, and microstructure of nanoreinforced cement pastes.
Two different types of MWCNTs, designated as “short” and “long”,
were used with an aspect ratio and surface area of 700 and 1600
and 110e250/300, respectively. Results from fracture mechanics
tests indicated that the fracture properties of the cementitious
matrix greatly improved in all cases. Higher concentrations of short
MWCNTs are required to achieve effective reinforcement, while
lower amounts of longer MWCNTs are needed to achieve the same
degree of mechanical performance. Nanoindentation results sug-
gested that MWCNTs can strongly reinforce the cement paste ma-
trix at the nanoscale by increasing the amount of high stiffness
CeSeH and decreasing the porosity. Sobolkina et al. [19] investi-
gated the effect of two types of MWCNTs, with their lengths being
different by one order of magnitude. The first type of MWCNTs
measured approximately 20 mm in length at a diameter of
approximately 1e15 nm; the length of second type typically
measured 100e300 mm with a diameter of approximately
15e40 nm. Dispersion of the 0.5 wt% MWCNT suspensions was
accomplished in water containing a surfactant and using a soni-
cator operated at an amplitude of 70% for 30, 150, and 210 min. The
authors conducted uniaxial quasi static and dynamic compression
and tensile tests. The modification of the cement pastes with the
dispersed MWCNTs led to an increase of up to 40% in compressive
strength and to a less than 10% increase in tensile strength under
high strain-rate loading. Marginal improvement and/or decrease in
compressive and tensile strength were observed for quasi static
loading. Collins et al. [20] reported the results of MWCNT disper-
sion on the consistency and strength of MWCNTeOPC pastes. The
authors observed a small variation in the measured mini-slump
values which however correspond to the variation in the aspect
ratio. The compressive strength results showed little variation be-
tween samples containing MWCNTs having almost the same aspect
ratio. A remarkable increase was observed in the nanocomposite
reinforced with a significantly lower aspect ratio MWCNTs. Abu Al-
Rub et al. [21] investigated the reinforcing effect of two different
types of MWCNTs (short and long) on the flexural strength, stiffness
and toughness of nanomodified cement pastes. The designated as
“short” MWCNTs had an average aspect ratio of about 157, whereas
the “long” MWCNTs had an average aspect ratio of 1250e3750.
Improvement in the flexural strength and ductility was observed
for all 28d specimens. Pastes reinforced with low concentrations of
long MWCNTs exhibited comparable mechanical performance to
the ones reinforced with higher concentration of short MWCNTs. It
was also noticed that for the same concentration the long MWCNT
nanocomposites showed higher strength and less ductility than the
corresponding short MWCNT nanocomposites, probably due to
breakage of the long nanotubes during the sonication process that
in turn leads to a relatively better dispersion of the MWCNTs. More
recently, Stynoski et al. [22] used dispersed pristine carbon nano-
tubes and silica-functionalized carbon nanotubes at an amount of
0.125 wt% in cement mortars. Both types of MWCNTs had the same
length and diameter. Their results showed that the use of silica
functional groups increased the fracture toughness of the MWCNT
mortars, indicating a stronger frictional bond between the matrix
and reinforcement. A stronger elastic bond was also shown by an
increase in the nanocomposite elastic modulus when silica func-
tional groups are used with MWCNTs.
Whilst the aforementioned studies so far concentrate in exper-
imentally determining either the effect of the aspect ratio of
MWCNTs or their chemical functionalization in the mechanical
properties of nanoreinforced cement pastes and mortars, there is
practically no information available in the literature about the ef-
fect of the bulk density of MWCNTs on the mechanical properties of
the cement-based nanocomposites. Results from the literature
suggest that reinforcing at the nanoscale with low bulk density
MWCNTs results in a more efficient and uniform dispersion in most
types of matrices. In polymeric matrices, the successful incorpo-
ration of low bulk density MWCNTs can lead to polymer nano-
composites exhibiting superior properties. The effect of the
MWCNTs's bulk density on the mechanical properties of high
density polyethylene nanocomposites was reported by Morcom
et al. [23]. The authors used 5 different types of MWCNTs including
thin, purified and COOH-functionalized MWCNTs with different
bulk densities. Experimental results from tensile tests, conducted
on dog-bone polyethylene nanocomposites, indicated that the
lower bulk density of MWCNTs would allow an easier path for the
polymer to infiltrate between the nanotubes and would also
improve the ability of these materials to be dispersed. The lower
the bulk density of MWCNTs the higher the mechanical properties,
with the polymer reinforced with the lower bulk density MWCNTs
exhibiting the higher improvement in both Young's modulus (66%)
and yield stress (69%).
Aside from the superior mechanical properties, the electrome-
chanical characteristics of MWCNTs open new potential applica-
tions for cementitious nanocomposites with added multi-
functionality. Results of experimental studies on MWCNT rein-
forced cementitious materials converge to the point that the
addition of carbon nanotubes improve the electrical properties of
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
individual MWCNTs and d is the equivalent fiber diameter.
Generally, for any given volume percentage of fibers of equal
length that can ideally be assumed uniformly distributed in a ma-
terial mix, the number of individual fibers per unit volume varies
inversely with the square of the individual fiber diameter and can
be calculated by using the following equation:
VIF
FC ¼
Vf
where the VIF is the volume of an individual fiber and Vf is the
volume fraction of the fiber per unit volume, which can easily
calculated by the equation:
Mf
Vf ¼
rB
where Mf is the fiber content, percent by mass and rB is the bulk
density of the fibers.
From the aforementioned determination of the MWCNT count
per unit volume, it is clearly observed that the MWCNT count de-
pends on the bulk density: the lower the bulk density the higher
the fiber count. The calculated MWCNT count for all mortar mixes is
presented in Table 2. The dispersion of MWCNTs is a challenging
procedure, primarily due to the strong interaction forces that cause
the entanglement and the formation of bundles in the pristine
MWCNTs. In this work, a simple, one step dispersion method
[32,33] was followed to achieve homogeneous dispersion of
MWCNTs in the cementitious mixture. In a typical dispersion pro-
cedure the MWCNT/suspensions are prepared by adding MWCNTs
to an aqueous polycarboxylate based surfactant solution, at a sur-
factant to nanotube weight ratio of 4.0. Ultrasonic energy is applied
to the suspensions by a 500 W cup-horn high intensity ultrasonic
processor with a standard probe of a diameter of 19 mm and a
temperature controller. The sonicator is operated at amplitude of
57% so as to deliver constant energy rate of 1900e2100 J/min, at
cycles of 20 s in order to prevent overheating of the suspensions.
The MWCNT/suspensions were then added into the OPC, sand at a
constant water to cement ratio w/c ¼ 0.5, and sand to cement ratio
s/c ¼ 3.0. Mixing of the materials was performed according to the
procedure outlined by ASTM 305 using a standard robust mixer
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
2.2. Testing procedure
2.2.1. Properties of fresh mortars
Flow tests were performed in compliance with ASTM C 1437 to
investigate the effect of incorporation of MWCNTs on the work-
ability of cement mortars. The experimental setup is shown in
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
Fig. 1a. The flow values were calculated according to the equation:
(2)
Dm  Dc
F¼  100% (4)
Dc
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
(3) setting using an automatic Vicat apparatus and following ASTM 191
(Fig. 1b).
2.2.2. Mechanical properties
Three point bending tests were conducted to assess the flexural
performance of the nanoreinforced mortars. 4  4  16 cm pris-
matic specimens were prepared using the mixing protocol
described previously, and tested in three-point bending at the age
of 3, 7 and 28 days. The test was performed using a 25 kN MTS
servo-hydraulic, closed-loop testing machine under displacement
control. The rate of displacement was kept as 0.1 mm/min. The
flexural toughness T is the energy required for the material to fail
and was determined by integrating the 3 point bending load-
deflection curve of the nanoreinforced mortars.
The compressive strength of the mortar nanocomposites was
determined on the halves of the prisms after the fracture of the
flexure specimens, according to ASTM C349 and ASTM C109. Prior
to subjecting them to the uniaxial compression test, the two halves
were examined for the presence of cracks that might have been
generated during the three point bending test. The test was per-
formed using a 250 kN MTS servo-hydraulic, closed-loop testing
machine under displacement control. The rate of displacement was
kept as 0.3 mm/s.
According to ASTM C348 and ASTM C349 the specimens that
result in strengths differing by more than 10% from the average
value of all test specimens made from the same sample and tested
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
at the same period were not considered in determining both flex-
ural strength and compressive strength. Following the above
mentioned procedure assures that the variations of the test results
are not significant and do not affect the conclusions.
2.2.3. Strain sensing-Piezoresistivity experiments
The piezoresistive behavior of 28 day mortar nanocomposites
was investigated using the four pole method while cyclic uniaxial
compressive loading was simultaneously applied to the specimens
from a hydraulic testing machine MTS with a 25 kN capacity. The
electrical resistance of the mortar nanocomposites was measured
using two digital multimeters (Fluke 289 AC/DC True RMS) with the
ability to measure mA and V, and a power supply unit (Mastech
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
outer electrodes and the power supply unit was used for the cur-
rent intensity measurements. To take into account the nature and
geometry of the nanocomposites, the resistance measurements
were converted to electrical resistivity (r) calculated as resistance
per unit length:
RS
r¼
L
where, R is the resistance of the nanocomposite, S the cross-section
area of the specimen and L the distance between the two inner
electrodes. The cyclic compressive loading of maximum 2 kN
(approximately 5 MPa) was applied to each specimen. Every
loading-unloading cycle had duration of approximately 120 s. The
values of load, voltage and current intensity were recorded every
1 s, with the experimental procedure lasting 600e800s for each
specimen.
3. Results and discussions
3.1. Micro and nano structural characterization of MWCNTs
Structural characterization of carbon nanotubes was carried out
with scanning electron microscopy (SEM), transmission electron
microscopy (TEM), and thermogravimetric analysis (TGA).
Fig. 2 shows representative SEM micrographs of pristine
MWCNTs (1000C1 and 1000C3), taken on a Zeiss SUPRA 35VP SEM
microscope. In all images, only bundles of multi-wall carbon
nanotubes are observed and there is no sign of any impurities e.g.,
amorphous carbon, which would be present in granular form.
Especially, as we can see in Fig. 2b, only the existing carbon
nanotubes are illustrated in a typical form of ribbon complexes.
The diameter of MWCNTs varies between 20 and 45 nm for
Fig. 2. SEM micrographs of pristine MWCNTs: (a) 1000C1, (b): 1000C3.
141
1000C1 grade and 20e40 nm for 1000C3 grade, as confirmed by the
TEM microscopy images shown in Fig. 3. The micrographs were
obtained in a Hitachi H7650 microscope.
Using Thermogravimetric Analysis (TGA) in air, the carbon
content of pristine MWCNTs was determined to be around 98.1% for
1000C1 (i.e. metal catalysts particle content ¼ 1.9%) and 94.6% for
1000C3 (Figs. 4 and 5, respectively), with the amount of amorphous
carbon in the carbon content being minimal for both cases. The
combustion of MWCNTs takes place at temperatures above 550  C,
whereas that of amorphous carbon at 300e350  C. The TGA anal-
ysis of functionalized MWCNTs in inert atmosphere (Fig. 6)
revealed a 5.5% wt% percentage of carboxyl groups in the 1001F
sample. A Perkin Elmer TGA 4000 was employed for the analysis.
3.2. Fresh properties of MWCNT reinforced mortars
Mortar flow is a relative measure of workability. Fig. 7 presents
the visual observation of the flow test of the plain mortar and the
0.1 wt% 1000C1, 1000C2 and 1000C3 MWCNTs mortar nano-
composites. As it can be seen from Fig. 7 and Table 3, the flow
spread of the MWCNT reinforced mortars decreased with the
MWCNT fiber count: the 1000C2 mortar mixture, which exhibits
(5)
the highest fiber count (12.9$1011) of individual MWCNTs assuming
perfect dispersion, exhibits the lowest flow spread (86%), followed
by the 1000C3 mortar (91%), and the 1000C1 mortar (102%), which
exhibits the lowest MWCNT count (3.6  1011). We should note at
this point that all these mixes contain superplasticizer (SP) to
promote stable dispersion through adsorption and surface accu-
mulation on the nanotubes' surface. Despite the fact that the water,
SP, cement and sand content is the same in all mortar mixtures,
higher fiber count mixes consume higher amount of SP, due to a
higher amount of individual MWCNTs. Therefore, a smaller amount
of SP remains available for interaction with the cement grains and
the mix appears to lose its workability.
The initial time of setting corresponds to the beginning of the
stiffening of the mortar and the loss of workability. When in contact
with water cement starts hydrating. It has long been recognized
that the use of polycarboxylate SPs may retard cement hydration.
As depicted from Fig. 8 the OPC mortar containing 0.4 wt% of
cement SP exhibits an initial time of setting of 2 h and 50 min. A
slight acceleration of the time of setting was observed for the
nanomodified 1000C1, 1000C2 and 1000C3 mortar mixtures when
compared to the plain mortar. Initial setting time for the mixture
reinforced with 0.1 wt% 1000C1 MWCNTs was approximately 2 h
and 25 min. The pristine 1000C2 nanomodified mortar and the
mechanically functionalized 1000C3 mortar exhibited an initial
setting time of 2 h and 15 min. Assuming that a good amount of SP
is adsorbed on the nanotubes surface, less amount of the SP is
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
compared with the neat mortar mix that contains the same amount
of SP. Therefore time of setting occurs a little earlier for all nano-
reinforced mortars [34].
3.3. Effect of the MWCNTs' aspect ratio, bulk density and
mechanical functionalization on strength, stiffness and energy
absorption ability of MWCNT reinforced mortars
Results of the three point bending tests of the flexural strength,
sf, of mortars reinforced with the two different types of pristine
MWCNTs (1000C1 and 1000C2) and the mechanically functional-
ized MWCNTs (1000C3) at an amount of 0.1 wt% of cement are
presented in Fig. 9. This particular amount of MWCNTs was found
from previous studies to produce mortar nanocomposites with
notably high mechanical and fracture properties [7,35,36]. All
MWCNT reinforced mortars exhibit higher flexural strength than
the plain mortar at all 3 ages. The mortars reinforced with the two
pristine MWCNTs, 1000C1 and 1000C2 exhibit a 78%, and 73% in-
crease in flexural strength respectively. Compared to the 1000C1
MWCNTs the smaller diameter and length of the 1000C2 MWCNTs
(Table 1) resulted in a smaller aspect ratio. On this basis, the
geometrical characteristics (and consequently the aspect ratio)
possibly play an important role in the reinforcing efficiency, in spite
of the fact that the count of individual MWCNTs that are theoreti-
cally uniformly distributed in the mortar matrix is twice as much as
the 1000C1 (Table 2). The highest improvement in the flexural
strength was seen in the mechanically functionalized 1000C3
MWCNTs specimens. This type of MWCNTs resulted by a manu-
facturer's mechanical functionalization of Type 1000C1 pristine
MWCNTs. As it is depicted from Table 1 types 1000C1 and 1000C3
have the same length, almost the same diameter, however type
1000C3 MWCNTs have remarkably lower bulk density. As discussed
above, geometrical parameters such as length and diameter, as well
as bulk density are used to calculate the fiber count of individual
fibers in a unit volume of cementitious matrix [31]. It is observed
from Table 2 that the count of well dispersed 1000C3 MWCNTs at
the amount of 0.1 wt% is approximately three times higher than the
count of 1000C1 MWCNTs (when dispersed at the same amount,
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).
The Young's modulus results of plain mortar and 0.1 wt%
1000C1, 1000C2 and 1000C3 MWCNT reinforced mortars are pre-
sented in Fig. 10. Similarly to the flexural strength results, the
Young's modulus impressively increases with the MWCNTs
incorporation. The 28d of the 0.1 wt% 1000C1 and 1000C2 MWCNT
nanoreinforced mortars exhibit a 87% and 84% increase in Young's
modulus respectively. Type 1000C3 MWCNT nanocomposite yields
the extraordinary increase of 124%. By comparison, it is obvious
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
3.4.1. Effect of MWCNT chemical functionalization on the fresh
properties of mortars
Chemical functionalization is usually used to tailor and enhance
the interaction of the nanotubes with the matrix. As mentioned
previously, type 1001F MWCNTs were developed by chemically
functionalizing pristine MWCNTs, so that the outer surface of the
nanotubes is modified by carboxylic groups COOH. This chemical
functionalization provides the MWCNTs with the ability to uni-
formly disperse in a material, and without the need of any soni-
cation procedure or additional dispersion means. In the following
analysis two nanoreinforced mortars were prepared and tested: (a)
mortars reinforced with effectively “dispersed” 1001F MWCNTs;
and (b) mortars reinforced with “as received” 1001F MWCNTs.
Fig. 16 shows pictures of suspensions prepared with 0.1 wt%
1001F MWCNTs “as received” and after the sonication procedure.
Many agglomerates can be seen on the “as received” 1001F sus-
pension container's walls. The flow spread of “dispersed” and “as
received” 0.1 wt% 1001F MWCNT reinforced mortars is presented in
Fig. 17. As it can be seen from Fig. 17 and Table 4, a lower workability
(92%) of the mortar mixture containing the “dispersed” chemically
functionalized MWCNTs was observed over the “as received”
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-
plied by the sonication helps the surfactant to further detangle the
nanotubes by steric or electrostatic repulsions [37]. Therefore, the
amount of individual MWCNTs in the “dispersed” suspension is
definitely higher than in the “as received” mix due to the applica-
tion of sonication energy. The flow behavior of the pastes and
mortars is mainly controlled by the dispersion of cement. When a
higher number of well dispersed MWCNTs is present in the mix
they potentially adsorb a higher amount of SP on their surface;
hence less amount of SP is available for the dispersion of cement in
the mortar matrix, which slightly affects the workability.
The time of initial setting for plain mortar and mortar reinforced
the chemical functionalized 0.1 wt% 1001F MWCNTs as received
and after the dispersion method is shown in Fig. 18. The sonication
procedure that the “dispersed” 1001F MWCNTs underwent helped
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
Fig. 15. Failure patterns of 28d (a) plain mortar and (b) 0.1 wt% 1000C3 MWCNT nanomodified mortar.
Fig. 16. Aqueous suspension containing the chemical functionalized 1001F MWCNTs
(a) “as received” and (b) “dispersed”.
Fig. 17. Flow test results of mortar mixes reinforced with (a) “dispersed” and (b) “as
received” 1001F MWCNTs at an amount of 0.1 wt% of cement.
147
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
included for comparison, as all three mortar mixes have the same
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
container's walls. These inclusions act as stress concentration areas,
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].
From the results presented in Fig. 19 it is also observed that
although types 1000C3 and 1001F MWCNTs present the same
nanotube count, both the “as received” and “dispersed” 1001F
MWCNT reinforced mortars consistently exhibited lower flexural
strength than the 1000C3 mortars. It is possible that the polar
functional groups such as eOH, eCeO, attached to the surface of
the 1001F MWCNTs, could lead to a slight decrease of the MWCNTs/
mortar interfacial interaction [38].
The Young's modulus results of the 0.1 wt% “dispersed” and “as
received” 1001F and 1000C3 MWCNT 28d mortars are presented in
Fig. 20. In general, Young's modulus follows the same trend as
flexural strength: The modulus of both the mechanically and
chemically functionalized MWCNT reinforced mortars is impres-
sively increased. However, despite the same MWCNT count, both
the “as received” and “dispersed” 1001F MWCNTs mortars exhibit a
lower increase compared to the 1000C3 reinforced mortars. It is
possible that the strong acid treatment can significantly disrupt the
MWCNT structure which can result in a reduction of the MWCNTs'
length during mechanical deformations [39]. It has been previously
reported that when MWCNTs are oxidized by a mixture of sulfuric
and nitric acids, their length can dramatically decrease [40]. As a
result, the interfacial length between the nanotubes and the matrix
becomes smaller. The weaker interfacial bonding can decrease the
stress transfer efficiency from the matrix to the nanotubes, when
loading is applied in the nanocomposite specimens [41].
3.5. Effect of fiber count and functionalization of MWCNTs on
strain-sensing
Piezoresistivity measurements were carried out to study the
effect of the fiber count and functionalization on the change of the
mortars' electrical properties and its ability to realize the change in
strain. The fractional change in resistivity was found to provide a
much more valuable indication of the change of the electrical
properties and the effect of functionalization. Results are presented
in Fig. 21. The addition of pristine 1000C1 MWCNTs was found to
have a great influence on the piezoresistive response as the 0.1 wt%
1000C1 MWCNT reinforced mortar yielded a fractional change in
resistivity, of about 10.6%. The addition of the mechanically modi-
fied 1000C3 MWCNTs and chemically modified “dispersed” and as
received 1001F MWCNTs however did not result in any piezor-
esistive response, despite the good dispersion, the higher aspect
ratio, the larger surface area and the higher count of individual
MWCNTs in the mortar matrix (Table 2). Mechanical and chemical
functionalization introduces structural defects and disrupts the
single and multiple bonds of electrons, in chemistry called as p-
conjugation system, in surface of carbon nanotubes; hence func-
tionalized MWCNTs do not always retain the electrical properties of
pristine MWCNTs [35,42,43]. Cho et al. [44] concluded that the
electrical conductivity of the surface-functionalized MWCNT
nanocomposites was lower than that of the pristine MWCNT-
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%
increase in flexural strength and a 86% increase in Young's modulus,
while the “as received” 1001F MWCNT reinforced mortars exhibi-
ted a 51% increase in flexural strength and a 75% increase in Young's
modulus, respectively. 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. This
functionalization provides the MWCNTs with the ability to uni-
formly disperse in a material, without the need of any sonication
procedure or additional dispersion means. The ultrasonication
energy provided to the “dispersed” 1001F MWCNTs helps the sur-
factant to further detangle the nanotubes by steric or electrostatic
repulsions. Therefore the “dispersed” 1001F MWCNTs appear to
have a more pronounced effect on reinforcing the mortar matrix.
On the other hand, it was found that functionalized MWCNTs do
not always retain the electrical properties of pristine MWCNTs. The
addition of the mechanically modified 1000C3 MWCNTs and
chemically modified “dispersed” and “as received” 1001F MWCNTs
did not result in any piezoresistive response, despite the good
dispersion, the higher aspect ratio, the larger surface area and the
higher count of individual MWCNTs in the mortar matrix. Me-
chanical and chemical functionalization introduces structural de-
fects and disrupts the single and multiple bonds of electrons,
(called as p-conjugation system), on the surface of carbon nano-
tubes; hence functionalized MWCNTs do not always retain the
electrical properties of pristine MWCNTs and strain sensing ability.
Acknowledgements
The authors would like to acknowledge the financial support of
the National Strategic Reference Framework (NSRF) - Research
Funding Program “SYNERGASIA 2011 - Nano-Modified Smart Con-
crete (NSC) (11SYN_5_1430)”, Partnerships of Production and
Research Institutions in Focused Research and Technology Sectors,
funded by the European Union (European Social Fund - ESF) and
Greek national funds through the Operational Program “Competi-
tiveness and Entrepreneurship and Regions in Transition (EPAN II)”.
TITAN Inc., and Sika Hellas Inc. are kindly acknowledged for sup-
plying the cement/sand and surfactant respectively. Finally, the
authors would also like to acknowledge the National Center of for
Scientific Research “Demokritos” (Athens, Greece) and the Foun-
dation for Research and Technology (Crete, Greece) for assisting
with the characterization of some of the MWCNT samples.
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