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Composites: Part A 70 (2015) 6981

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Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

Review

Review of nanocarbon-engineered multifunctional cementitious


composites
Baoguo Han a,, Shengwei Sun b, Siqi Ding a, Liqing Zhang a, Xun Yu c, Jinping Ou a,b,
a
School of Civil Engineering, Dalian University of Technology, Dalian 116024, China
b
School of Civil Engineering, Harbin Institute of Technology, Harbin 150090, China
c
Department of Mechanical & Energy Engineering, University of North Texas, Denton, TX 76203, USA

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

Article history: As structural materials, cementitious materials are quasi-brittle and susceptible to cracking, and have no
Received 27 August 2014 functional properties. Nanotechnology is introduced into cementitious materials to address these issues.
Received in revised form 3 December 2014 Nano materials, especially nano carbon materials (NCMs) were found to be able to improve/modify the
Accepted 5 December 2014
mechanical property, durability and functional properties of cementitious materials due to their excellent
Available online 19 December 2014
intrinsic properties and composite effects. Here, this review focuses on the recent progress of fabrication,
properties, and structural applications of high-performance and multifunctional cementitious composites
Keywords:
with NCMs including carbon nanobers, carbon nanotubes and nano graphite platelets. The improve-
A. Discontinuous reinforcement
A. Smart materials
ment/modication mechanisms of these NCMs to composites are also discussed.
B. Physical properties Crown Copyright 2014 Published by Elsevier Ltd. All rights reserved.
B. Microstructures

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
2. Brief introduction to three types of NCMs used for fabricating NFCC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3. Dispersion of NCMs in cementitious composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
4. Properties of NFCC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
4.1. CNTs/CNFs enhanced/modified cementitious composites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
4.1.1. Mechanical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
4.1.2. Electrical and sensing properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
4.1.3. Other properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
4.2. NGPs enhanced/modified cementitious composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
5. Characterization methods for NFCC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
5.1. Characterization methods of dispersion of NCMs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
5.2. Characterization methods of performances of composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
6. Enhancement/modification mechanisms of NCMs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
6.1. Enhancement/modification mechanisms of CNTs/CNFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
6.2. Enhancement/modification mechanisms of NGPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
7. Structural applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
8. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79

Corresponding authors. Tel./fax: +86 411 84780087.


E-mail addresses: hanbaoguo@dlut.edu.cn (B. Han), oujinping@hit.eud.cn (J. Ou).

http://dx.doi.org/10.1016/j.compositesa.2014.12.002
1359-835X/Crown Copyright 2014 Published by Elsevier Ltd. All rights reserved.
70 B. Han et al. / Composites: Part A 70 (2015) 6981

1. Introduction provide a systematical review on major progresses and advances


in the fabrication, properties and mechanism, and structural appli-
Cementitious materials are the most commonly and widely cations of NFCC.
used construction materials for various types of infrastructures.
However, cementitious materials are in general very brittle, and
2. Brief introduction to three types of NCMs used for fabricating
characterized by low tensile strength and low strain to failure
NFCC
[1]. Since macroscopic steel bars were used to reinforce the cemen-
titious materials, the size of the reinforcing llers has diminished
CNTs are allotropes of carbon with a hollowly cylindrical nano-
from macro scale to micro even nano scale with the development
structure. They are generally a few nanometers in diameter and
of nanotechnology. The addition of these tiny llers not only
several microns in length. According to the number of rolled layers
improves mechanical properties and durability of cementitious
of graphene, CNTs are categorized as single-walled CNTs (SWCNTs)
materials, but also endues them with such functionalities as elec-
and multi-walled CNTs (MWCNTs) [16]. Like CNTs, CNFs are also
trical, thermal and electromagnetic properties [2,3]. For example,
the quasi-one-dimensional carbon material, and their diameters
the fracture toughness of cementitious composites can be
are between those of CNTs and carbon bers (CFs). The representa-
enhanced by 400% when nano-ZrO2 is used as llers [4]. An addi-
tive properties of CNTs and CNFs are listed in Table 1. NGPs are car-
tion of 5% nano-Al2O3 can increase the elasticity modulus of
bon-based conductive nano-particles made from graphite.
cementitious composites by 143% [5]. The electrical resistance of
Graphene oxide (GO) is a single layer of NGPs that have been oxi-
cementitious composites can be decreased by 45% with 5% nano-
dized to intersperse the carbon layers with oxygen molecules. The
Fe2O3 [5]. Nano-TiO2 can endow cementitious materials with the
structures of NGPs are two-dimensional platelets consisting of a
photocatalytic effect to decompose both organic pollutants and
few to several graphene layers with an overall thickness in nano-
oxides such as NO, NO2 and SO2 [6]. Moreover, due to their remark-
meter scale and the particle diameter ranging from submicron up
able mechanical, electrical and thermal properties, excellent nano-
to 100 lm [13,17,18]. Typical properties of NGPs are also given
scale effects, low density, and excellent chemical and thermal
in Table 1.
stability, nano carbon materials (NCMs) offer the possibility to
develop a new generation of tailored, high-performance, and mul-
tifunctional cementitious composites[5,79]. Extensive research 3. Dispersion of NCMs in cementitious composites
endeavors demonstrated the potential of various NCMs including
carbon nanobres (CNFs), carbon nanotubes (CNTs) and nano Because the strong Van der Waals forces cause the agglomera-
graphite platelets (NGPs) for enhancing/modifying cementitious tion of the nano-particles, a key issue in fabricating high-quality
materials [1015]. For example, Li et al. observed that an addition NFCC is to homogeneously disperse NCMs in cementitious materi-
of 0.5 wt.% CNTs can improve the exural, compressive strength als. Poor dispersion will lead to the formation of defects in the
and the failure strain of the composites by 25%, 19% and 27%, matrix and limit the nano-enhancement/modication effect [27].
respectively [11]. Raki et al. reported that CNTs can improve the A lot of research work has been done to improve the dispersion
Vivtorinox hardness of the early hydration of composites by of NCMs in the cementitious composites. Commonly, there are
600%, the Young modulus by 227% and the exural strength by two types of methods used to disperse NCMs. One method is to
40% [7]. Gao et al. found that the compressive strength of compos- mechanically separate the NCMs by adopting ultrasonic [28
ites with 0.16 wt.% CNFs is 42.7% higher than that of the plain 39,4155,5763,6572,7476], ball milling [56,77]or high-shear
cementitious materials [12]. Huang obtained a maximum increase mixing technologies. The other method chemically alters the sur-
of 82% in the exural strength by adding NGPs into cementitious face of the NCMs by using covalent [11,36,59,61,74]or noncovalent
materials [13]. NCMs achieve the enhancement effect by nucle- modication approaches [35,36,4052,54,55,5873,75,76]. More-
ation, increasing the amount of CSH gel of high hardness, over, the mechanical methods are often used in combination with
improving pore structures, controlling nanoscale cracks, improving the chemical methods [10,14,2934].
the early strain capacity and reducing autogenous shrinkage of Recently, researchers have proposed some novel approaches to
cementitious composites [514]. These mechanisms would also solve the dispersion issue of NCMs. The primary approach is to
improve the durability of the cementitious materials [15]. In addi- adopt commonly used water reducing admixtures (including plast-
tion, due to their excellent electrical, thermal and electromagnetic icizers and superplasticizers) as surfactants. The research at the
properties, NCMs can impart electrical, thermal, electromagnetic National Research Council Canada has shown that a small amount
and sensing properties to cementitious materials [13,14]. of CNTs can be dispersed by ultrasonication in the water contain-
During the past decade, considerable research effort has been ing 5% superplasticizer [14]. Shah et al. also achieved an effective
directed towards the development of cementitious composites dispersion of MWCNTs with different lengths and concentrations
with NCMs, and many innovative achievements have been in cementitious materials by applying polycarboxylate-based
gained in both development and application of the NCMs lled superplasticizers [3739]. Yazdanbakhsh et al. performed a
cementitious composites (NFCC). The aim of this paper is to three-dimensional simulation study, and stated that only when

Table 1
Properties of NCMs [1,13,1726].

Property CNTs CNFs NGPs


MWCNTs SWCNTs
Elastic modulus/TPa 0.31 1 0.40.6 1 (in-plane)
Strength/GPa 1060 50500 2.77.0 1020
Electrical resistivity /lX cm 550 55 50 (in-plane)
Dimensions Diameter: 230 nm Diameter: 0.753 nm Diameter: 50200 nm Diameter: 120 lm
Length: 0.150 lm Length: 150 lm Length: 50100 lm Thickness: 30 nm
Surface area/m2/g >400 200 2630
Aspect ratio 1000 100500 50300
B. Han et al. / Composites: Part A 70 (2015) 6981 71

cement particles are also distributed homogeneously without any [35], lots of researches have been done to ascertain mechanical
agglomeration, the degradation effect of cement particles on the properties of CNTs/CNFs lles cementitious composites. These
homogeneous distribution of CNTs within cementitious materials researches and their results are summarized in Tables 2 and 3.
is negligible [78]. Meanwhile, Han et al. pointed out that the effec- The mechanical properties of NFCC are closely related to not only
tive dispersion of superplasticizers to CNTs/CNFs can be contrib- the type, the concentration, the surface condition and the disper-
uted to their double-dispersion effect on CNTs/CNFs and cement sion quality of CNTs/CNFs, but also the composition of cementi-
particles [19]. Huang also employed superplasticizer to obtain a tious materials. As shown in Tables 2 and 3, the observed best
proper dispersion of NGPs in cementitious materials [13]. There- performance enhancement of NFCC include a 300% increase in
fore, the dispersion of NCMs with water reducing admixtures is compressive strength [25], a 34.28% increase in tensile strength
an excellent method for fabricating NFCC without adding any addi- [91], a 269% increase in exural strength [44], a 270% increase in
tional dispersants that impair the hydration or mechanical proper- fracture toughness [41], a 14% increase in fracture energy [87,88],
ties of composites. However, this method only can improve the an over 600% improvement in Vickerss hardness at the early ages
dispersion effect to some extent because of the limit of dispersion of hydration [35], a 2200% increase in deection [74], a 130%
capability for water reducing admixture, and it needs high energy increase in ductility [44], an over 430% improvement in resilience
consumption due to use of ultrasonic treatment. Nasibulin et al. [23]and a 227% increase in Youngs modulus[40]. In addition, it
put forward a new method to solve the dispersion problem of should be noted that the addition of CNTs/CNFs also changes the
CNTs/CNFs, which is to make CNTs/CNFs and cement/mineral mechanical constitutive relations of composites (as shown in
admixture a whole by in-situ growing CNTs/CNFs on the cement, Fig. 1(b) and (c)).
mineral admixture particles or sand [14,7986]. Generally, the dis-
persion of NCMs in cementitious composites is still a critical issue. 4.1.2. Electrical and sensing properties
It is necessary to nd more simple, repeatable, large-scale and low- The addition of CNTs/CNFs decreases the electrical resistivity of
energy consumption methods for distributing NCMs in cementi- cementitious composites to nearly 1 X cm and increases their elec-
tious composites without altering the manufacturing process of trical conductivity by maximally about 8 orders of magnitudes
composites. against the plain one (as shown in Fig. 2a)) [56]. Just like the
mechanical properties of cementitious composites, their electrical
4. Properties of NFCC conductivities are also strongly dependent on the type, the concen-
tration, the surface condition and the dispersion quality of CNTs/
4.1. CNTs/CNFs enhanced/modied cementitious composites CNFs, and the composition and water contents of cementitious
materials [14,19,46,97104]. Meanwhile, the CNTs/CNFs
4.1.1. Mechanical properties enhanced/modied cementitious composites also exhibit sensitive,
Since early investigations showed that CNTs have strong effect stable and repeatable response of electrical property to external
on the hydration process and hardness of cementitious composites force or deformation [14,19,9799]. Recently, much effort has been

Table 2
Enhancement of CNTs to mechanical properties of cementitious materials.

Mechanical properties Enhancement in properties Concentration of CNTs Researchers


SWCNTs MWCNTs
Hardness 600% 2 wt.% Makar et al. [35]
177% 0.1 wt.% Ibarra et al. [40]
Tensile strength 34.28% 0.3 wt.% Ludvig et al. [91]
19% 0.5 wt.% Hunashyal et al. [92]
Tensile modulus 70.9% 0.5 wt.% Hunashyal et al. [92]
Compressive strength 19% 0.5 wt.% Li et al. [11]
70% 0.05 wt.% Yakovlev et al. [93]
11.03% 0.02 wt.% Keriene et al. [48]
50% 0.0450.15 wt.% Cwirzen et al. [36]
29.5% 0.2 wt.% Luo et al. [62]
25% 0.5 wt.% Collins et al. [45]
1020% 0.5 wt.% Musso et al. [60]
22% 0.1 wt.% Bharj et al. [57]
25% No given Hlavcek [87]
200% No given Nasibulin et al. [94]
30% 0.15 wt.% Kim et al. [64]
Flexural strength 25% 0.5 wt.% Li et al. [11]
10% 0.0450.15 wt.% Cwirzen et al. [36]
11.23% 0.004 wt.% Keriene et al.[48]
34% 0.5 wt.% Musso et al. [60]
43.75% 0.75 wt.% Hunashyal et al. [58,92]
269% 0.2 wt.% Al-Rub et al. [44]
35.45% 0.2 wt.% Luo et al. [62]
25% 0.048 wt.% and 0.08 wt.% Konsta-Gdoutos et al. [49]
Fracture toughness 149.32% 0.5 wt.% Luo et al. [63]
Ductility 130% 0.2 wt.% Al-Rub et al. [44]
28% 0.5 wt.% Hunashyal et al. [92]
Fracture energy 14% No given Hlavcek [87]
Modulus of toughness 154% 0.04 wt.% Al-Rub et al. [44]
Fracture modulus 34.7% 0.5 wt.% Musso et al. [60]
Critical opening displacement 34.96% 0.5 wt.% Luo et al. [63]
Youngs modulus 45% 0.048 wt.% and 0.08 wt.% Konsta-Gdoutos et al. [49]
50% 0.048 wt.% and 0.08 wt.% Shah et al. [38]
227% 0.1 wt.% Ibarra et al. [40]
72 B. Han et al. / Composites: Part A 70 (2015) 6981

Table 3
Enhancement of CNFs to mechanical properties of cementitious materials.

Mechanical properties Enhancement in properties Concentration of CNFs Researchers


Ductility 35.1% 1.0 vol.% Howser et al. [73]
73% 0.1 wt.% Al-Rub et al. [42]
Resilience 430% 1.0 wt.% Yazdanbakhsh [23]
Stiffness 25% 0.1 wt.% Al-Rub et al. [42]
Deection 34.9% 1.0 vol.% Howser et al. [73]
2200% 0.04 vol.% Peyvandi et al. [74]
Tensile strength 2226% 0.2 wt.% Gay et al. [72]
Compressive strength 300% 0.4 wt.% Nasibulina et al. [25]
21.4% 1 vol.% Gao et al.[95]
42.7% 0.16 wt.% Gao et al. [12]
Flexural strength 82% 0.2 wt.% Tyson et al. [41]
46% 0.04 vol.% Peyvandi et al. [74]
250% 1.0 wt.% wt.% Yazdanbakhsh et al. [70]
60% 0.1 wt.% Al-Rub et al. [42]
45% 0.048 wt.% Shah et al. [71]
Fracture toughness 270% 0.2 wt.% Tyson et al. [41]
Impact resistance 280% 0.04 vol.% Peyvandi et al. [74]
Energy sorption 3400% 0.04 vol.% Peyvandi et al. [74]
Abrasion weight loss 1700% 0.04 vol.% Peyvandi et al. [74]
Modulus of toughness 170% 0.1 wt.% Al-Rub et al. [42]
Peak displacement 150% 0.2 wt.% Tyson et al. [41]
Ultimate normalized capacity 30.7% 1.0 vol.% Howser et al. [73]
Youngs modulus 50% 0.048 wt.% Shah et al. [71]
68% 1.0 wt.% Yazdanbakhsh [23]

(a) Stress-strain diagrams for cementitious (b) Load vs. mid-span deflection relationships for
composites with 0.04% short MWCNT and 0.1% CNTs enhanced/modified cementitious composites
long MWCNT under compression [44] under bending [96]

Fig. 1. Mechanical properties of typical CNTs/CNFs lled cementitious composites. (For interpretation of the references to color in this gure legend, the reader is referred to
the web version of this article.)

done on the sensing behavior (as shown in Fig. 2b)) of cementitious by 20% (from 0.07 W/m K to 0.056 W/m K) [93]. Veedu stated that
composites with different types and concentrations of CNTs/CNFs the thermal performance of CNTs lled cementitious composites is
under different loading types, loading speeds, loading frequencies, at least 35% and 85% higher than that of the CFs lled and the
temperatures, humidies (or water contents), etc. [14,19,46,95,97 unmodied ones respectively [65]. Al-Rub et al. found that incor-
104]. poration of CNTs treated by the functional groups (COOH and
OH) produces an improvement to workability of the cementitious
4.1.3. Other properties composites [42]. Shukla et al. studied the smoke detection prop-
Damping, thermal, electromagnetic interference (EMI) and erty of composites with MWCNTs, and found that the DC transient
other properties of CNTs/CNFs enhanced/modied cementitious studies depict an increase in electrical conductivity when exposed
composites were also investigated. For example, Luo observed that to smoke [106]. Keriene et al. observed that the non-autoclaved
the frequency responses function (FRF) amplitude (i.e. damping aerated concrete and the autoclaved aerated concrete with
ratio) of composites increases with increased content of MWCNTs MWCNTs are more stable during exploitation than those compos-
(as shown in Fig. 3a)) [62,105]. Han et al. found that even a very ites without these additions [48]. In addition, Singh et al. found
small dosage of MWCNTs can effectively improve the transport that the high value of EMI shielding effectiveness (SE) of MWCNTs
properties (i.e. water sorptivity) of the composites. The test was lled cementitious composites is dominated by absorption rather
performed by allowing one surface of the specimen to be in contact than reection. An addition of 0.6 wt.% MWCNTs into cementitious
with water of 10 mm depth using a circular plexiglas support materials can lead to a 27% decrease in electromagnetic wave
through recording the weight of the specimen at xed time inter- reectivity at a frequency of 2.9 GHz (as shown in Fig. 3c))
vals (as shown in Fig. 3b))[15]. Yakovlev et al. observed that the [56,66]. Gong et al. studied the effects of CNTs on the dielectric
addition of CNTs decreases the heat conductivity of foam concretes and piezoelectric properties of PZT cementitious composites. The
B. Han et al. / Composites: Part A 70 (2015) 6981 73

(a) Electrical conductivity of CNTs filled cementitious composites [56]

(b) Sensing property of cementitious (c) Sensing property of cementitious composites with
composites with CNTs under CNFs under bending [22]
compression[100]

Fig. 2. Electrical and sensing properties of typical CNTs/CNFs lled cementitious composites. (For interpretation of the references to color in this gure legend, the reader is
referred to the web version of this article.)

dielectric constant and the dielectric loss increase with CNT con- [77]. Peyvandi et al. investigated the contributions of NGPs to the
tent (as shown in Fig. 4a)), while the piezoelectric strain factor durability of cementitious composites, and observed that NGPs sig-
and the piezoelectric voltage factor both only increase with the nicantly improve the moisture transport performance and acid
CNT content up to 0.3 vol.%. The highest piezoelectric strain factor resistance of the composites at a low dosage (0.05 vol.%) [24].
and piezoelectric voltage factor values are 62 pC/N and From these research results, it has been proved that NCMs can
60  10 3 Vm/N, which are respectively 41% and 28% higher than signicantly enhance/modify the mechanical and functional prop-
that of the composites without CNTs (as shown in Fig. 4b)) [107]. erties of cementitious composites at a low concentration. However,
the existing researches mainly focus on the enhancement/modi-
cation effects of NCMs on performance parameters of different
4.2. NGPs enhanced/modied cementitious composites
cementitious composites. It is necessary to set up some constitu-
tive models for describing and predicting performances of NFCC,
Huang et al. observed that the addition of NGPs increases the
and discover the hidden connections between different perfor-
exural strength of cementitious composites by 82% compared
mances of the composites. In addition, previous researches mainly
with the plain ones. The electrical property of the composites is
investigated the enhancement/modication effect of NCMs to
signicantly modied, and the composites become highly conduc-
cementitious composites without coarse aggregate. However, the
tive (as shown in Fig. 5) [13]. However, compared with Fig. 2a), it is
cementitious composite with coarse aggregate, i.e. concrete, is
obvious that the contribution of NGP content to the electrical prop-
much more useful in real applications. It deserves extensive inves-
erty of the composites is less than that of the same addition of
tigation on the enhancement/modication of NCMs to concrete.
CNTs. Duan et al. reported that only 0.05% GO can improve the ex-
ural strength of cementitious composites from between 41% to 59%
and the compressive strength from between 15% to 33% [108]. Lv 5. Characterization methods for NFCC
et al. found that GO nanosheets can remarkably increase the
tensile/exural strength of the corresponding cementitious com- Advances in material characterization techniques and computa-
posites. Especially, when the content of GO is 0.03%, the tensile, tional material science have provided us with promising new tools
exural and compressive strength of cementitious composites to better understand and engineer the structure of NFCC and to
increases by 78.6%, 60.7% and 38.9%, respectively [109]. enhance/modify properties of cementitious composites.
Du et al. studied the sensing behavior of NFCC with different
contents of NGPs (04.8 wt.%), and observed that the composites 5.1. Characterization methods of dispersion of NCMs
exhibit a decrease in electrical resistivity and present a good sens-
ing property when NGP content is in the range from 2.4 vol.% to There are two approaches for characterizing dispersion of
3.6 vol.% [110]. Singh et al. found that the SET (total SE) of the NCMs. One is to observe the solution of NCMs with advanced
GO-ferrouid-cementitious composites is 46 dB, which is much instruments such as optical microscopy, scanning electron micro-
higher than that of the pristine cementitious composites (4 dB) scope (SEM), transmission electron microscopy (TEM), Fourier
74 B. Han et al. / Composites: Part A 70 (2015) 6981

(b) Relationships between water absorbing amounts


(a) Representative frequency responses of CNT
and water absorbing time of cementitious materials
enhanced/modified cementitious composites
with and without CNTs (#0 = 0% CNT, #1 = 0.2%
with 0.1% (DMd1), 0.2% (DMd2), 0.5%
CNT + NaDDBS, #2 = 0.2% CNT + SDS. The
(DMd5), 1.0% (DM1) and 2.0% (DM2) of
zoom-out is experimental setup for water sorptivity
CNTs
test. (Q is the volumetric flow rate (m3/s), A is the
cross sectional area perpendicular to the flow
direction (m2)) [15]

(c) Shielding effectiveness (SE) in the frequency range


from 8.2 to 12.4GHz of cementitious composites
with 0, 1, 2, 3, 4, 5, 10 and 15 wt.% of MWCNTs
(OPC, CCNT1-15)[56]

Fig. 3. Other properties of typical CNTs/CNFs lled cementitious composites. (For interpretation of the references to color in this gure legend, the reader is referred to the
web version of this article.)

(a) Dielectric constant and dielectric loss of PZT (b) Piezoelectric strain factor and piezoelectric
cementitious composites with various CNT contents voltage factor of PZT cementitious composites
[107] with various CNT contents [107]

Fig. 4. Dielectric and piezoelectric properties of typical CNTs lled cementitious composites.
B. Han et al. / Composites: Part A 70 (2015) 6981 75

of load, deection and position with the AFM tip indenting over the
surface of the cementitious composites so that the mechanical
properties of the composites can be measured using the nanoin-
dentation module. In addition, some numerical methods such as
representative elementary volume, numerical analysis, two-
dimensional micromechanical simulations and the nite element
methods, also have been employed to assist in analyzing the com-
pressive strength, tensile strength, cracking strength, bending force
and shear force of NFCC (as shown in Fig. 6b)) [96,112116].
Because the compositions, structures and processing technology
of NFCC are complex in nature, the existing techniques still cannot
realize the full analysis of the properties and microstructures of
NFCC. More advanced tools are needed to help to characterize,
understand and control the structures and properties of NFCC.
Fig. 5. Electrical resistivity of cementitious composites with GNP (i.e. NGPs) [110]
(For interpretation of the references to color in this gure legend, the reader is 6. Enhancement/modication mechanisms of NCMs
referred to the web version of this article.).

6.1. Enhancement/modication mechanisms of CNTs/CNFs

transform infrared spectroscopy, Raman spectroscopy, energy dis- The enhancement/modication of CNTs/CNFs on the properties
persive X-ray spectrum, environment scanning electron micro- of cementitious composites mainly results from the extensive dis-
scope, ultraviolet visible spectroscopy, X-ray photoelectron tribution enhancement network of CNTs/CNFs in composites [56].
spectroscopy, small angle light scattering and atomic force electron Generally, the following factors have contributions to the
microscopy [11,41,5356,60,75,93]. However, the dispersion of mechanical property of composites: (1) Excellent intrinsic proper-
NCMs in solution cannot fully represent the dispersion of NCMs ties of CNTs/CNFs (as shown in Table 1); (2) The nano size effect
in composites. The other one is to observe the distribution of NCMs and nucleation effect of the CNTs/CNFs including small size effect,
in composites through the microanalysis methods, which include surface effect and high aspect ratio. Makar and Chan observed that
atomic force electron microscopy, SEM, TEM, environment scan- the CNTs appear to act as nucleating sites for the C3S hydration
ning electron microscope, laser ablation inductively coupled products (as shown in Fig. 7a)) [117], thus accelerating the hydra-
plasma mass spectrometry and so on [35,52,53,55,60,75,93]. In tion reaction of the C3S (as shown in Fig. 7b)) and increasing the
addition, some researchers tried to employ numerical simulation amount of high stiffness CSH gel (as shown in Fig. 7c)) [52];
methods (3-D simulations and probability density function calcu- (3) Improvement of CNTs/CNFs to microstructures and the interfa-
lation) to realize fully determination of the dispersion of NCMs cial transition zone of composites. For example, the autogenous
[78,111]. shrinkage in composites with CNTs reduces at least 30% after
96 h compared with composites without CNTs (as shown in
5.2. Characterization methods of performances of composites Fig. 7d)). Furthermore, the addition of CNTs/CNFs nes pore size
distribution and decreases the porosity (or nanoporosity) of com-
In order to investigate the behaviors in nanoscale of NFCC and posites by lling the gaps (or pores) between the hydration prod-
the improvement/modication mechanisms of NCMs to cementi- ucts such as CSH gel and ettringite. Therefore, the composites
tious materials, some advanced instruments including X-ray dif- become much more compacted [11,14,52,118,119]; (4) Strong
fraction, atomic force electron microscopy, mercury intrusion bonding between CNTs/CNFs and the matrix, especially for the
porosimetry and the accelerated surface area and porosimetry sys- covalence-modied CNTs/CNFs. For example, Peyvandi et al.
tem have been used to measure the hydration products, hardness, employed hydrophilic groups (COOH) covalence-modied CNFs
Youngs modulus, porosity and pore size distribution of the com- to improve interfacial interactions in composites, in which the
posites [11,40]. For example, Fig. 6a shows the records of the data COOH groups form strong coordinate bonds with the Ca2+ ions in

(a) Three-dimensional topographic image of AFM (b) Comparison between simulation and
scanning over CNTs enhanced/modified experimental load-deflection response of CNTs
cementitious materials [40] cementitious composites [96]

Fig. 6. Test and simulation of properties of typical NFCC. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this
article.)
76 B. Han et al. / Composites: Part A 70 (2015) 6981

Cement sonicated with CNT


Sonicated cement
Cement

(a) TEM images of CNTs (b) Relationship between heat flow and hydration time of cementitious
within the hardened materials (The numbers in Figure identify the peaks as: 1 initial C3A
cementitious composites [44] reactions; 2 C3S surface reactions; 3 the main C3S hydration peak; and 4
ettringite formation) [117]

(d) Comparison of autogenous shrinkage of


(c) Amount of high stiffness C-S-H of cementitious cementitious composites with and without CNTs
composites with CNT [52] [119]

(e) Bonding between modified CNFs with cementitious material [90]

(f) CNF pulled out from a microcrack (g) CNTs embedded in cementitious materials
bridging a crack [44]

Fig. 7. Enhancing effect of CNTs/CNFs to cementitious materials. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of
this article.)

cement hydrates, thus enhancing the mechanical properties of To the conductive and sensing property, the factors that may
composites (as shown in Fig. 7e)) [90]; (5) Crack bridging, pinning make contributions mainly include the intrinsic electrical conduc-
effect, ber pull-out, crack deection, ber debonding and ber tivity, contacting conduction, tunneling conduction and eld emis-
breaking (as shown in Fig. 7(f) and (g)) [14,44]. sion conduction of CNTs/CNFs (as shown in Fig. 8) [14,120122].
B. Han et al. / Composites: Part A 70 (2015) 6981 77

Fig. 8. Schematic diagram of basic conductive element in conductive network of CNTs cementitious composites [122]. (For interpretation of the references to color in this
gure legend, the reader is referred to the web version of this article.)

Actually, the conduction mechanism of CNTs/CNFs enhanced/mod- radiation penetrating inside the shield but also increases the effec-
ied cementitious composites is very complex in nature. The tive absorption capability. Therefore, the CNTs/CNFs embedded in
above-mentioned conduction mechanisms coexist in composites concrete matrix increase the interfacial polarization and the effec-
and interrelate each other. One or several factors among these tive anisotropy energy of composites, thus leading to the high SE of
aspects may be dominant for a specic NFCC. In general, the con- NFCC [56,66].
ductive characteristic of NFCC can be described by the percolation The enhancement of CNTs to the piezoelectric and dielectric
phenomenon. In addition, the electrical resistivity of NFCC would properties of PZT cementitious composites can be attributed to
change when the composites deform under loading. The factors the following reasons, i.e. the CNTs act as conductive llers dis-
that may contribute to the sensing property include (1) the change persed in the cement matrix, improving the poling efciency of
of intrinsic resistance of CNTs/CNFs; (2) the change of bonding the PZT cementitious composites and enabling the poling process
between CNTs/CNFs and matrix; (3) the change of contact between to be carried out at room temperature, in contrast to the 120 C
CNTs/CNFs; and (4) the change of tunneling distance between required for the PZT cementitious composites without CNTs [107].
CNTs/CNFs. It should be noted that the above-mentioned factors
usually work together for the contribution to sensing property of 6.2. Enhancement/modication mechanisms of NGPs
NFCC, but only one or several of them are leading at certain perco-
lation zones (i.e. content levels of CNTs/CNFs). Therefore, the per- As a type of nano-particles with two-dimensional structure,
colation threshold is an important parameter for designing and NGPs possess the small size effect that enables NGPs to serve
optimizing the sensing property of NFCC. Generally, the CNTs/CNFs as nuclei. For example, GO nanosheets could regulate formation
concentration above the percolation threshold is benecial for the of ower-like crystals (as shown in Fig. 10). The formed network
sensing sensitivity under tension, while that below the percolation structure of cement hydration products around the NGPs can
threshold is benecial for the sensing sensitivity under compres- improve the homogeneity and compactness of the hardened
sion [14]. cementitious composites. For example, additions of 0.05% GO
The presence of conductive CNTs/CNFs in the insulative cemen- decrease the total porosity of cementitious composites from
titious matrix results in space charge accumulating at the inter- 32.6% to 28.2% (as shown in Fig.11). NGPs also have the surface
faces, which contributes towards the higher microwave effect, which leads to enormous interface areas. At the interfaces,
absorption in the composites [56]. The dielectric constant increases NGPs possess an intimate bonding with the cement matrix due to
with the MWCNT content. This improves the capability of the com- strong Van der Waals forces. The large aspect ratio and plate shape
posites to shield electromagnetic waves (as shown in Fig. 9). The of NGPs give themselves strong abilities to block and divert the
increase in MWCNT leads to a reduction of skin depth and an micro cracks, which can slow down crack propagation and forma-
increase in AC conductivity along with an improvement of input tion of the crack network. The bridge effect of NGPs can delay crack
impedance. This not only enhances the amount of electromagnetic origination and prevent crack opening up. In addition, NGPs also

(a) variation of dielectric constant (b) dielectric loss


Fig. 9. Behavior of dielectric constant of MWCNT enhanced/modied cementitious composites with 0, 1, 2, 3, 4, 5, 10 and 15 wt.% of MWCNTs (OPC, CCNT1-15)[56]. (For
interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)
78 B. Han et al. / Composites: Part A 70 (2015) 6981

Fig. 10. Schematic diagram of regulation mechanism of GO on cement hydration crystals [109].

The action mechanism of NGPs on the EMI property of NGPs


enhanced/modied cementitious composites is similar to that of
CNFs/CNTs enhanced/modied cementitious composites [77].
Overall, the above researchers observed some evidences to
explain the enhancement/modication mechanism of NCMs to
cementitious composites. However, these evidences just provided
qualitative or descriptive explanations, because their contributions
to performances of the composites are complex in nature. There-
fore, it is necessary to try to build up useful quantitative correla-
tions between the components, processing or microstructures
and the properties of NFCC.

7. Structural applications
Fig. 11. Pore size and distribution of GO enhanced/modied cementitious com-
posites [108]. (For interpretation of the references to color in this gure legend, the The current applications of NFCC mainly focus on two aspects.
reader is referred to the web version of this article.)
One aspect is to enhance mechanical performances and durability
of structures or structural components (e.g. concrete beams, col-
can enhance mechanical properties of these composites via the umns and pipes). For example, Hunashyal et al. investigated the
crack-arresting effect and the improvement to the interfacial tran- behavior of beams fabricated with MWCNTs enhanced/modied
sition zone of NFCC [13]. cementitious composites [58]. The exural strength of the beam
For the electrical property of NFCC, Huang proposed several the- is increased by 43.75% at MWCNT addition of 0.75 wt.%. Gao
ories on the mechanism of the contributions of NGPs to cementi- et al. employed CNFs in cylinders to enhance the mechanical prop-
tious materials based on the characteristics of NGPs. NGPs have erties. The peak compressive strength of the cylinders increases by
the pi-electrons that participate in interlayer pi bonding. This 21.4% when the CNF concentration is 1%. Moreover, the stiffness of
makes NGPs become a good electrically conductive material. In the cylinders containing CNFs is much higher than that of the plain
addition, the carbonation process with temperature up to ones [95]. Peyvandi et al. added the modied NGPs into the dry-
1050 C during fabrication of NGPs leaves a large excess of holes cast concrete pipes in aggressive sanitary sewer environment to
in the valence band. Due to this characteristic of NGPs, they con- improve their durability characteristics including the moisture
tribute to the electrical property of NFCC through the following sorptivity and acid resistance, thus increasing their service life in
paths: (1) Electronic conduction and hole conduction through sanitary sewer applications [24].
NGPs by the tunneling effect; (2) Electronic conduction and hole The other one aspect is to use their functional performances for
conduction through contacting conduction of NGPs [13]. The two structural health monitoring or trafc detection [123]. For exam-
factors both contribute to the electrical property of NFCC, but ple, Howser et al. built shear-critical columns with cementitious
one of them may be dominant for certain content of NGPs. composites containing CNFs. The columns are capable of strain
B. Han et al. / Composites: Part A 70 (2015) 6981 79

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Further reading
and mechanical properties of cement composites. Constr Build Mater
2013;49:1217. [89] Nasibulina LI, Anoshkin IV, Nasibulin AG, et al. Effect of carbon nanotube
[110] Du H, Quek ST, Dai P S. Smart multifunctional cement mortar containing aqueous dispersion quality on mechanical properties of cement composite. J
graphite nanoplatelet. Proc. SPIE 8692. 2013. p. 869238. Nanomater 2012;169262:6.