Advances in Cement Research Advances in Cement Research, 2015, 27(1), 1121

Volume 27 Issue 1 http://dx.doi.org/10.1680/adcr.13.00058

Paper 1300058
Characterisation and simulation of highly Received 24/08/2013; revised 23/02/2014; accepted 06/05/2014
dispersed carbon nanofibre-reinforced Published online ahead of print 17/07/2014

cement materials ICE Publishing: All rights reserved

Wang, Zhang, Ge and Zhu

Characterisation and simulation of

highly dispersed carbon nanofibre-
reinforced cement materials
Bao-Min Wang Shu-Kui Ge
Associate Professor, Institute of Building Materials, Dalian University of Engineer, Liaoning Building Science Research Institute, Shenyang, China
Technology, Dalian, China Yu Zhu
Yuan Zhang Engineer, Liaoning Building Science Research Institute, Shenyang, China
Postgraduate, Institute of Building Materials, Dalian University of
Technology, Dalian, China

In this work, carbon nanofibres (CNFs) were incorporated into ordinary Portland cement matrices. The mechanical
behaviour of these composites and the effect of CNFs on cement hydration and microstructure of cement paste were
compared with a plain cement sample by means of mercury intrusion porosimetry, X-ray diffraction, thermal analysis
and scanning electron microscopy. The random distribution of CNFs in cement matrices was simulated by three-
dimensional Monte Carlo method. The results showed that the added 0 .1 wt% CNFs increased the maximum flexural,
compressive strength, toughness and impermeability performance of blended cement compared with the samples.
The incorporation of CNFs into cement paste accelerated the rate of the hydration reaction and increased the amount
of hydration products. The use of CNFs also improved pore parameters, and the pore size distribution of these
composites shifted towards smaller pore size scope. In addition, scanning electron micrographs showed that good
interaction between CNFs and the cement matrix occurs, with CNFs acting as fillers, resulting in a denser micro-
structure.

Introduction
Cement is a highly popular choice of material and is used in vast
quantities worldwide owing to its low cost and ready availability.
Cement is typically characterised as quasi-brittle and having low
tensile strength. When the concrete is loaded, initial and discon-
tinuous microcracks appear in this matrix. Conventional fibres
can overcome these weaknesses and can significantly improve the
mechanical properties (Chen et al., 2004; Silva et al., 2010; Yang
and Li, 2010). However, these fibres cannot stop the initiation of
cracks on a nanoscale. The development of nanosized fibres, such
as multi-walled carbon nanotubes (MWCNTs) and carbon nano-
fibres (CNFs), has created a new and extensive field to control
the matrix cracks at the nanoscale, and essentially create a new
generation of a crack-free material (Konsta-Gdoutos et al.,
2008, 2010a; Shah et al., 2009).
CNFs, whose outer surface usually consists of conically shaped
graphite planes canted with respect to the longitudinal fibre axis,
are considered one of the most beneficial nanomaterials for
nano-reinforcement (Lawrence et al., 2008; Tibbetts et al.,
2007). The Youngs modulus of an individual CNF is around
400 GPa and its average tensile strength is approximately 7 GPa
(Zhou et al., 2009). Their attractive properties make them
potential candidates in a wide range of applications, such as
biomedical science, field emission, super capacitors, molecular
sensors and composites (Han et al., 2010; Liu et al., 2010; Lu
et al., 2012; Marsh et al., 2012; Wang et al., 2013b; Yun et al.,
2010).
Previous research on CNFs and MWCNTs in cement matrices
has focused on enhancing their mechanical properties. Abu Al-
Rub et al. (2012) and Tyson et al. (2011) found that the treated
CNFs improved the mechanical properties of hardened cement
paste, whereas deterioration was found in cement/surface-treated
CNFs composites. Sanchez (2009) and Sanchez and Ince (2009)
found that silica fume improved the dispersion and interfacial
interaction of CNFs in a matrix. Furthermore, CNFs enhanced
the splitting tensile strength and durability of cement/CNFs
composites. Metaxa et al. (2009, 2013) demonstrated that the
addition of CNFs greatly enhanced the flexural strength, Youngs
modulus, toughness and autogenous shrinkage of cement ma-
trices. However, most research has focused on the compressive of
splitting tensile strength (Chaipanich et al., 2010; Collins et al.,
2012), and only a little work has been done on the flexural
strength of these composites (Konsta-Gdoutos et al., 2010b;
Wang et al., 2013a).
This paper presents an investigation that was carried out on
the mechanical behaviour and impermeability performance of
these composites and the effect of CNFs on cement hydration
and microstructure of cement paste. At the same time, the
degree of cement hydration and the amount of hydration

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Advances in Cement Research Characterisation and simulation of highly
Volume 27 Issue 1 dispersed carbon nanofibre-reinforced
cement materials
Wang, Zhang, Ge and Zhu

products were calculated by X-ray diffraction (XRD) and
thermal analysis (TG/DSC). The deterioration of pore param-
eters and morphology of these composites were studied
through mercury intrusion porosimetry (MIP) and ultra-high-
resolution field emission scanning electron microscopy (FE
SEM). Finally, the random dispersion of CNFs in the cement
matrix was analysed by three-dimensional (3D) Monte Carlo
simulation.
Experimental method
Materials
The CNFs (length, 10,50 m; diameter, 100,150 nm) used in
this study were provided in Japan by Showa Denko K.K. Co., Ltd
(price: US$ 0.3/g). The physical parameters are shown in Table 1
and their morphology is shown in Figure 1. The commercially
available surfactant methylcellulose (MC) was supplied by She-
nyang Sinopharm Chemical Reagent Co., Ltd, China. The poly-
carboxylate-based water-reducing agent (superplasticiser) was
supplied by Dalian Mingyuanquan Group Co., Ltd, China, and
the defoamer was liquid tributyl phosphate (TBP) (supplied by
Tianjin Chemical Reagent Plant, China). The cement was pro-
duced by Dalian Onoda Cement Co., Ltd and the oxide composi-
tion is shown in Table 2.
Specimen preparation
According to previous research (Wang et al., 2012), CNFs were
dispersed in aqueous solution by applying ultrasonic energy with
the chosen surfactant (MC) and the optimum MC to CNFs ratio
of 2:1 by concentration was required to achieve dispersions with
maximum achievable dispersion of CNFs in the aqueous MC
solution. The weighed CNFs were put into the aqueous surfactant
solutions and the homogeneous CNF suspensions were gained
after ultrasonic processing (DS-3510DT, Shanghai Sonxi Ultra-
sonics Instrument Co., Ltd, China, operating frequency 40 kHz,
power 180W) for 15 min.
The prepared homogeneous CNF suspension, defoamer and super-
plasticiser were mixed with cement in a multispeed planetary
mixer for 7 min. All the cement specimens were poured into the
40 3 40 3 160 mm3 moulds, and an electric vibrator was used to
ensure good compaction. These cement paste samples, covered
with a polyethylene film, were kept at 100% relative humidity for
24 h. After 1 d, the hardened cement pastes were demoulded and

Length: m Diameter: nm Ash: % Special surface area: m2/g Bulk density: g/cm3 Electric conductivity: cm

10,50 100,150 ,0 .01 90,120 0 .04 0 .01

Table 1. Physical parameters of CNFs

Hollow core

CVD layer

Catalytic
layer
2 m 2 m 50 nm

(a) (b) (c)

Figure 1. The morphology of CNFs

Calcium oxide: Silicon dioxide: Aluminium oxide: Iron (III) oxide: Sulfur trioxide: Magnesium oxide: Na2Oeq: %
% % % % % %

61 .13 21 .45 5 .24 2 .89 2 .50 2 .08 0 .77

Table 2. Chemical composition of P .O 42 .5R cement

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Volume 27 Issue 1 dispersed carbon nanofibre-reinforced
cement materials
Wang, Zhang, Ge and Zhu

cured in a lime-saturated bath for 27 d. In this study, six batches
of cement paste mixtures were prepared. These included a
reference cement paste and five batches of mixes with 0 .05,
0 .075, 0 .1, 0 .125 and 0 .15 wt% CNFs. The dosage of CNFs was
the mass percent of cement and the water to cement ratio was
0 .35. The mix proportion of these samples is shown in Table 3.
Testing procedures
After 28 d of curing, the flexural strength tests were performed in
a computer-controlled electro-hydraulic servo universal tester
(MTS318) according to Chinese Standard GB/T 17671-1999
(China National Standards, 1999). The average strength value of
the prepared three samples per batch was reported and the
crosshead rate was 0 .20 mm/min. Then the separated two parts
were used to test the compressive strength. The loading rate on
these samples was 2400 N/s. Toughness tests were performed by
a three-point bending test in a computer-controlled electro-
hydraulic servo universal tester (MTS318) with a crosshead speed
of 0 .10 mm/min according to the standard ASTM C1018-97
(ASTM, 1997).
According to ASTM C1585 (ASTM, 2013), three cylindrical
specimens (50 mm high and 100 mm in diameter) were used in
the permeability test, with one surface exposed to water and all
other surfaces covered by a plastic sheet. All specimens were
weighed after 1, 5, 10, 20 and 30 min, 1, 2, 3, 4, 5 and 6 h, and
1, 2, 3, 4, 5, 6, 7, 8 and 9 d. The wet surface of the specimens
was towel dried and the weight was measured before the re-
exposure procedure.
After the flexural and compressive strength tests, these samples
were soaked in ethanol to stop the hydration reaction, and then
dried in an oven at 508C for about 24 h. Six samples were tested
by using an automated mercury porosimeter (Autopore IV 9500
series, Micromeritics Instrument Corp., USA), with two low-
pressure stations plus one high-pressure station, and with a
maximum pressure of 33 000 psia for pore size measurements.
Fine cement/CNFs composites powder samples (particle size of
80 m) were used in this study. The XRD analysis was carried by
an automatic X-ray powder diffractometer (D/MAX-2400, Rigaku
Ltd, Japan) with CuK radiation at 35 kV and 25 mA over the
2 range from 108 to 708 at room temperature. The scan rate was
0 .58/min, and the phase analysis of these samples was made by
using MDI Jade 5.0 evaluation software.
Meanwhile, cement/CNFs composite powder samples were pre-
pared for thermal analysis (TG/DSC) by a thermal analysis
instrument (Mettler Toledo Stare, Mettler Toledo Co., Ltd,
Switzerland). These samples were heated from room temperature
to 10008C at a heating rate of 108C/min in a nitrogen atmosphere.
The thermal analysis was made by using Stare software. The mass
loss of these composites occurring at about 1108C and 4708C
mainly responds to the decomposition of calcium silicate hydrates
(C-S-H) and calcium hydroxide (Ca(OH)2), respectively. The
content of calcium silicate hydrates and calcium hydroxide can
be calculated by Equations 1 and 2 (Knapen and Van Gemert,
2009; Pacewska et al., 2011; Zhao et al., 2013). WLC-S-H (%) and
WLCa(OH)2 (%) are the mass loss during the decomposition of
calcium silicate hydrates and calcium hydroxide shown in the TG
curve. MW C-S-H , MW Ca(OH)2 and MW H2 O are the molecular mass
of calcium silicate hydrates, calcium hydroxide and water at 28 d
(i.e. 182 .32 g/mol, 74 g/mol and 18 g/mol), respectively (Zhao et
al., 2013).
MW C-S-H
W C-S-H (%) WLC-S-H (%) 3
1: MW H2 O
MW Ca(OH)2
W Ca(OH)2 (%) WLCa(OH)2 (%) 3
2: MW H2 O
The morphology study was performed using ultra-high-resolution
FE SEM (Nova NanoSEM 450, FEI Co., Ltd, USA) at an
accelerating voltage of 3 kV with 40,400 000 magnification.
Before this SEM observation, the prepared samples
(1 3 10 3 10 mm) were coated with an approximately 20 nm
thick gold film layer. Furthermore, energy dispersive spectroscopy
(EDS) (Oxford INCA-7260, FEI Co., Ltd, USA) was used to
study the dispersibility of CNFs in the cement paste.

Sample Water to cement ratio Mix proportion: wt%

CNFs MC TBP Superplasticiser

CF-0 0 .35 0 0 0 .15 0 .1

CF-1 0 .35 0 .05 0 .1 0 .15 0 .1
CF-2 0 .35 0 .075 0 .15 0 .15 0 .1
CF-3 0 .35 0 .1 0 .2 0 .15 0 .1
CF-4 0 .35 0 .125 0 .25 0 .15 0 .1
CF-5 0 .35 0 .15 0 .3 0 .15 0 .1

Table 3. The mix proportion of cement/CNFs composites

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Volume 27 Issue 1 dispersed carbon nanofibre-reinforced
cement materials
Wang, Zhang, Ge and Zhu

sample, the flexural and compressive strengths of each of the

Results
Flexural and compressive strength
The mean values of flexural and compressive strength of
hardened cement paste incorporating CNFs at 28 d of hydration
are shown in Figure 2. Basically, compared to the reference
sample, flexural and compressive strength both improve as CNFs
content increases until it reaches the optimal amount of 0 .1%
(i.e. 23 .95% and 5 .02% improving rate), and then they start to
drop. The enhancement of these cement/CNFs composites is
attributed to the addition of CNFs. The crosslink of CNFs with
cement hydration products resists the formation of microcracks.
However, at a relative high concentration of CNFs, the CNFs are
easily agglomerated in the mixes and a weak bond between
agglomerated CNFs and partial hydration products is formed
(Luo et al., 2011). Additionally, CNFs may not be wetted
properly thus causing fibre pullout, resulting in the formation and
propagation of microcracks (Morsy et al., 2011).
To have a better understanding of the influence of the added
surfactant, a comparative experiment was conducted by adding
CNFs and surfactant individually. Compared to the reference
14
12
Flexural strength: MPa
prepared samples were a little lower than those of the reference
sample, which is shown in Figure 3. The average flexural and
compressive strengths of the sample with individual surfactant
(sample CF-S) were 8 .67 and 70 .7 MPa, which indicated that the
added surfactant delayed the hydration of cement and increased
the porosity. Moreover, without the assistance of surfactant, the
CNFs were easy to bundle together in the matrix. The agglomer-
ated CNFs weakened the distribution of hydration products in the
matrix, and the effective bridging effect improved the mechanical
performance of samples, which deteriorated the ultimate mech-
anical properties of cement/CNFs composites eventually (sample
CF-C).
High toughness properties
Table 4 shows the results of the toughness performance of the
prepared samples, including first crack initiation, maximum peak
loading, fracture energy and displacement. The addition of CNFs
increases all the toughness indices of Portland cement pastes.
Compared to the reference sample, the toughness indices in-
creased and then started to drop. The maximum enhancement
was obtained by sample CF-3, which incorporated 0 .1 wt% CNFs
in the matrix. The added 0 .1 wt% CNFs increased first crack
initiation, maximum peak loading, fracture energy, displacement
of the samples by 125 .8%, 49 .7%, 174 .7% and 114 .9%,

10
14
8 12
Flexural strength: MPa

6 10
4 8

2 6

0 4
0 0050 0075 0100 0125 0150
CNFs ratio: % 2
(a)
0
CF-0 CF-3 CF-S CF-C
76 (a)

75
Compressive strength: MPa

76
Compressive strength: MPa

74
74
73
72
72
70
71
68
70
66
69
0 0050 0075 0100 0125 0150
64
CNFs ratio: % CF-0 CF-3 CF-S CF-C
(b) (b)

Figure 2. Flexural and compressive strength of hardened cement Figure 3. Flexural and compressive strength of comparative
paste containing CNFs experiment at 28 d

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Volume 27 Issue 1 dispersed carbon nanofibre-reinforced
cement materials
Wang, Zhang, Ge and Zhu

Sample CNFs ratio: wt% First crack initiation: Maximum peak loading: Fracture energy: N/m Displacement: mm
mm kN

CF-0 0 0 .097 2 .285 92 .63 0 .154

CF-1 0 .05 0 .148 2 .436 137 .02 0 .227
CF-2 0 .075 0 .154 2 .719 170 .94 0 .246
CF-3 0 .1 0 .219 3 .420 254 .42 0 .331
CF-4 0 .125 0 .184 3 .208 231 .09 0 .296
CF-5 0 .15 0 .126 2 .485 127 .05 0 .207

Table 4. Toughness indices of the prepared cement/CNFs

composites

respectively. Moreover, the mixes with CNFs ratio of 0 .15 wt%

15
showed a slight enhancement. The full loaddeflection curves of
each prepared cement/CNFs composite are presented in Figure 4.

Impermeability performance 10
Length: mm

Figure 5 shows the rate of permeability test of prepared cylindrical

specimens with different proportions of reinforcement by CNFs. CF-0
The specimens that incorporated CNFs had lower permeability CF-1
rates, which can be attributed to the control and delay effect of 05 CF-2
CNFs in the matrix. Moreover, the addition of CNFs improved the CF-3
pore parameters, which decreased the porosity and the composites CF-4
became compacted. Sample CF-3 incorporating 0 .1 wt% CNFs CF-5
showed the best impermeability performance. However, the 0
sample CF-5 had a similar permeability performance to the 0 200 400 600 800
reference sample, which was caused by the loss of mix work- Time: s1/2
ability of the cement paste and the increased pore parameters.
Figure 5. Rate of permeability tests of samples with different
proportions of reinforcement CNFs at 28 d
Porosity and pore size distribution
MIP was widely applied to characterise the pore structure param-
eters of cement pastes, for example pore size distribution, pore
Differential intrusion: ml/g per mm

volume and porosity (Chen and Wu, 2013; Nochaiya and CF-0
Chaipanich, 2011). Figure 6 shows the variation of differential 00015 CF-1
intrusion with pore diameter, and the total pore characterisation is CF-2
CF-3
summarised in Table 5. It can clearly be seen that the addition of
00010 CF-4
4 CF-5

00005

3 CF-1
CF-5 0
CF-3 10 000 1000 100
Load: kN

Pore size diameter: nm

2
Figure 6. MIP analysis of porosity and pore size distribution of
CF-0 CF-4 cement/CNFs composites
1
CF-2
CNFs decreased the porosity and reduced the pore size of
0 cement/CNFs composites. This trend is similar to those for the
0 01 02 03 04 flexural and compressive strengths. The average pore diameter
Deflection: mm
(APD) of the reference sample is about 58 .5 nm, whereas the
Figure 4. Loaddeflection analysis of prepared samples at 28 d APD values of composites are much lower, about 39 .7, 30 .7,
22 .0, 26 .8 and 26 .4 nm.

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Advances in Cement Research Characterisation and simulation of highly
Volume 27 Issue 1 dispersed carbon nanofibre-reinforced
cement materials
Wang, Zhang, Ge and Zhu

Sample Total intrusion Total pore Median pore Median pore Average pore Apparent Porosity: %
volume: ml/g area: m2/g diameter diameter (area): diameter: nm (skeletal)
(volume): nm nm density: g/ml

CF-0 0 .1205 8 .232 77 .3 46 .3 58 .5 2 .2590 21 .3931

CF-1 0 .0958 9 .644 57 .8 27 .0 39 .7 2 .3638 18 .4614
CF-2 0 .0925 12 .079 55 .0 17 .2 30 .7 2 .3241 17 .7437
CF-3 0 .0830 15 .095 38 .8 11 .5 22 .0 2 .3344 16 .2224
CF-4 0 .0901 13 .451 49 .1 13 .7 26 .8 2 .3017 17 .1762
CF-5 0 .0918 13 .907 50 .2 13 .9 26 .4 2 .3229 17 .5732

Table 5. MIP analysis of cement/CNFs composites at 28 d

For CF-0, with the decrease of pore size, differential intrusion phases can be found in these XRD patterns, which indicates that
increased and reached the maximum value of about 0 .0013 ml/g the presence of CNFs cannot change the type of cement hydration
per nm at the pore size diameter of 77 .1 nm, and then started to products.
drop. Other mixes showed the same trends and these maximum
values of differential intrusion appeared in the much finer region Moreover, it is clear that the phase composition of the cement/
of pores, which indicates that the added CNFs reduce the pore CNFs composites exhibits a strong surface interaction between
size. CNFs and cement hydration products. This strong surface inter-
action is further shown by the intensity peak values and the new
As a kind of porous material, hardened cement paste has a lower peaks aroused over the 2 range from 108 to 408, and eventually
mechanical property for its weaker pore characterisation. The it increases the load transfer efficiency from CNFs to cement
addition of CNFs improves the pore characterisation of these paste in case of tension.
composites. Ultimately, the flexural and compressive strength of
the composites is ameliorated. The intensity, crystal size of calcium hydroxide in CF-0 and CF-3
are 139 cps, 57 .4 nm and 199 cps, 49 .0 nm, respectively, which
XRD analysis suggests that the calcium hydroxide in CF-3 is composed of a
The effect of CNFs on the cement paste was evaluated by relatively high degree of crystallisation crystals with smaller
comparing the intensities of XRD diffraction peaks. At the curing crystal size. The addition of CNFs accelerates the hydration of
period of 28 d, XRD patterns of CF-0 and CF-3 are shown in cement paste.
Figure 7. Some important phases in the process of the cement
hydration reaction can be found in Figure 7 (El-Didamony et al., Thermal (TG/DSC) analysis
2012; Jumadurdiyev et al., 2005; Mendes et al., 2011). No new The TG/DSC analysis of the hardened samples CF-0 and CF-3,
registered at 28 d of hydration, are shown in Figure 8. Four mass
1 losses can be detected in the TG curve, responding to decomposi-
tion of calcium silicate hydrates, ettringite, calcium hydroxide
1
and calcium carbonate respectively. Correspondingly, there are
2 four endothermic peaks in the DSC curve. The four endothermic
1 CF-3
1 4 1 peaks are located at 1108C, 1508C, 4708C and 7108C, respectively
3 1
4 (Hidalgo et al., 2009; Petkova et al., 2012).

1 1 The amounts of calcium silicate hydrates and calcium hydroxide

2 content in CF-0 and CF-3 are presented in Table 6. In the
1 samples CF-0 and CF-3 at a curing period of 28 d, the amounts
4
1 CF-0
3 1 of calcium silicate hydrates and calcium hydroxide content are
24 .18%, 13 .57% and 34 .77%, 13 .95%, respectively. Higher
amounts of calcium silicate hydrates and calcium hydroxide
10 20 30 40 50 60 70
2: deg content than those of the reference sample can be found in the
mixed composites. This indicates that the incorporation of CNFs
Figure 7. MIP XRD patterns of CF-0 and CF-3 composites at 28 d in cement pastes accelerates the hydration reaction of the cement
of hydration: 1 calcium hydroxide, 2 calcium carbonate, paste, which increases the amount of calcium silicate hydrates
3 ettringite, 4 tricalcium silicate content and finally improves the mechanical properties of the
hardened cement/CNFs composites.

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Volume 27 Issue 1 dispersed carbon nanofibre-reinforced
cement materials
Wang, Zhang, Ge and Zhu

100 2
CF-0 00004 matrix including calcium, oxygen, aluminium, silicon, magne-
00002 sium and potassium. The raw quantitative data corresponding to
80
0 0 the spectrum given in Figure 10 are shown in Table 7, which

DSC: mW/mg

DTA: mg/C
60 00002 confirms the added CNFs and the cement phases.
TG: %

00004
2
40 00006 3D Monte Carlo simulation
00008 The dispersion effect of CNFs in the cement matrix by analytic
20 TG 00010 analysis is very challenging because of the complexity in
DSC 4
DTA 00012 quantifying the shape and random orientation distribution in
0
200 400 600 800 1000 composites. In most composite simulations (Dendievel et al.,
Temperature: C 2006; Foygel et al., 2005; Li et al., 2007; Vassal et al., 2008), a
(a)
soft core model is employed to allow the intersection among
100 CF-3 0 CNFs/CNTs in a 3D representative volume element (3D RVE).
0 However, this model apparently goes against the physical princi-
80 00002
ple that CNFs/CNTs can never penetrate through each other
DSC: mW/mg

00004
DTA: mg/C

2 partially or completely. In this study, the hard-core model was

60
TG: %

00006 applied to simulate the dispersion of CNFs in the matrix. The

40 4
position and the orientation of CNFs are assumed to follow a
00008
random distribution and the CNFs are assumed to be identical in
20 TG 00010 shape, as shown in Figure 11(a). The details of this simulation by
DSC 6
DTA 00012 using Matlab software are as follows (Yu et al., 2010, 2013).
0
0 200 400 600 800 1000
Temperature: C (a) Define a 3D cubic RVE.
(b) (b) Define a single CNF, and it will be assigned in the RVE
completely. The parameters (i.e. starting point, length,
Figure 8. Thermal analysis of composites at curing period of 28 d diameter, ending point, generated angle) will also be
determined.
(c) Define the shortest distance between any two CNFs. The
shortest distance will not be less than the diameter of CNFs.
No. Dosage of CNFs: Calcium silicate Calcium (d ) Define the parameters of the cement matrix.
% hydrate: % hydroxide: %
For example, with an aspect ratio of 100, the dispersion effect of
CF-0 0 24 .18 13 .57
CNFs in the cement matrix is shown in Figure 11(b). The CNFs
CF-3 0 .1 34 .77 13 .95
are randomly distributed in the cement matrix, and this simulated
Table 6. Amounts of calcium silicate hydrate and calcium silicate result is helpful for the further simulation calculation regarding
hydrate content in composites at 28 d mechanical, conductivity and piezoresistivity properties.

Microstructure and EDS analysis
It is believed that the higher mechanical properties of these
cement/CNFs composites are attributable to the contribution of
CNFs where they can fill between the hydration products such as
calcium silicate hydrates and ettringite. FE SEM micrographs of
CF-3 at a curing period of 28 d are shown in Figure 9. CNFs are
embedded in cement hydration products, which act as networks
and bridges across the pores and cracks (Figures 9(a) and 9(b)).
CNFs are tightly wrapped by calcium silicate hydrates (Figure
9(c)), which indicates that high bonding strength is achieved.
Furthermore, CNFs have been pulled out but without rupture
failure (Figure 9(d)), which ensures the load transfer in tension to
improve their mechanical properties.
Additionally, the EDS spectrum of CF-3 is shown in Figure 10
and it exhibits the CNFs and other elements comprising cement
Conclusion
A comparative study was made of the mechanical properties, pore
parameters, cement hydration and microstructure of hardened
cement paste in the presence of CNFs. The results showed that
the addition of CNFs improved the mechanical properties of
cement pastes. The maximum improvement in flexural strength
and compressive strength were obtained by the hardened cement
paste incorporating CNFs at a concentration of 0 .1% (i.e. 23 .95%
and 5 .02% improving rate). Moreover, the added 0 .1 wt% CNFs
increased first crack initiation, maximum peak loading, fracture
energy and displacement of the samples by 125 .8%, 49 .7%,
174 .7% and 114 .9%, respectively. The addition of CNFs also
improved the impermeability performance of prepared cement
samples. The incorporation of CNFs in cement paste accelerated
the hydration reaction and increased the amount of hydration
products at the curing period of 28 d. Furthermore, the addition
of CNFs improved the pore parameters of cement/CNFs compo-
sites. The hardened cement pastes with CNFs had a lower

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Advances in Cement Research Characterisation and simulation of highly
Volume 27 Issue 1 dispersed carbon nanofibre-reinforced
cement materials
Wang, Zhang, Ge and Zhu

(a) (b)

(c) (d)

Figure 9. Typical FE SEM micrographs of CF-3 after 28 d of

curing

Element CF-3 composites Reference sample

Weight: % Atomic: % Weight: % Atomic: %

Carbon 8 .95 15 .14 0 .73 1 .12

Oxygen 48 .62 61 .74 50 .47 67 .32
Silicon 7 .41 5 .36 9 .81 8 .91
Potassium 0 .89 0 .46 1 .72 1 .25
Calcium 34 .13 17 .30 37 .27 21 .38
Total 100 .00 100 .00

Table 7. Elemental analysis of EDS mapping from cement/CNFs

composites and reference sample

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Advances in Cement Research Characterisation and simulation of highly
Volume 27 Issue 1 dispersed carbon nanofibre-reinforced
cement materials
Wang, Zhang, Ge and Zhu

CNFs

100 m X
(a)
(a)

Ca
O
K
Ca
C Si
K

0 2 4 6 8 10
(b)

Figure 10. EDS analysis of sample CF-3

porosity, pore diameter and a higher total pore area than those of
the reference sample. The microstructure of cement/CNFs com-
posites showed that the embedded CNFs act as the bridges and
networks across voids and cracks, which ultimately increases the
load transfer in tension. (b)

Furthermore, investigation of the dispersion effect of CNFs in the
cement matrix is performed by the method of 3D Monte Carlo
simulation. This simulated result is helpful to obtain a better
understanding of the dispersion effect of CNFs and the further
simulation calculation of mechanical, conductivity and piezo-
resistivity properties.
Acknowledgements
The authors would like to express appreciation for the financial
support by the National Natural Science Foundation of China
(51278086), the Program for New Century Excellent Talents in
University by Ministry of Education of the Peoples Republic of
China (NCET-12-0084), China Petroleum Science and Technol-
ogy Innovation Fund Project (2013D-5006-0606), Liaoning Bai-
Figure 11. (a) The position and the orientation of CNFs in RVE;
(b) dispersion effect of CNFs in cement matrix by using Matlab
software
QianWan Talents Program (2012921073), Dalian Plan Projects of
Science and Technology (2012A13GX024, 2013A16GX113),
Dalian Projects of Construction Technology (201307) and the
Construction Safety and Environment State Key Laboratory Open
Fund (201202).
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