Construction and Building Materials 133 (2017) 9197

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Construction and Building Materials

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Review

Applications of using nano material in concrete: A review

M.S. Muhd Norhasri a,, M.S. Hamidah b, A. Mohd Fadzil c
a
Faculty of Civil Engineering, Universiti Teknologi MARA, Cawangan Pulau Pinang, Malaysia
b
Faculty of Civil Engineering, Universiti Teknologi MARA, Shah Alam, Malaysia
c
Institute of Infrastructure and Sustainable, Engineering and Management (IIESM), Universiti Teknologi MARA, Shah Alam, Malaysia

h i g h l i g h t s

 An overview from the past and current research highlights regarding nano materials in concrete.
 Provide knowledge on the nano materials and application in enhancing human life.

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

Article history: This review paper discussed on the nano materials in concrete. Nowadays, the application of nano mate-
Received 25 May 2016 rials has received numerous attentions to enhance the conventional concrete properties. Eventually, the
Received in revised form 30 November 2016 introduction of nano materials in concrete is to increase its strength and durability. Nano material is
Accepted 2 December 2016
defined as material that contains particle size which less than 200 nm. For the purpose of concrete study,
the application of nano materials must be at least 500 nm in size. The addition of ultrafine nano material
will help to reduce the cement content by partially replacing cement on weight basis to improve the
Keywords:
binding effect. The ultrafine particles of nano material will also help reduce the formation of micro pores
Nano material
Nano silica
by acting as a filler agent, producing a very dense concrete and automatically reduce the growth of micro
Nano alumina pores in the UHPC structures. Moreover, this paper presents on the advantages and benefits to enhance
Nano kaolin the concrete by utilizing nano materials.
Nano clay 2016 Elsevier Ltd. All rights reserved.

Contents

1. Background of concrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
2. Development of nano concrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
3. Production of nano materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
4. Application of nano materials in UHPC. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
5. Nano silica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
6. Nano alumina . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
7. Carbon nano tube (CNT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
8. Polycarboxylates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
9. Titanium oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
10. Nano kaolin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
11. Nano clay . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
12. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95

Corresponding author.
E-mail addresses: norhasri@gmail.com (M.S.M. Norhasri), hmidsaman@yahoo.
com (M.S. Hamidah), fadiil2013@yahoo.com (A.M. Fadzil).

http://dx.doi.org/10.1016/j.conbuildmat.2016.12.005
0950-0618/ 2016 Elsevier Ltd. All rights reserved.
92 M.S.M. Norhasri et al. / Construction and Building Materials 133 (2017) 9197
1. Background of concrete
Evolution of concrete has started from normal grade concrete
from grade 545 [1,2]. Those grades were popular in 1900s for
construction purposes and provide adequate strength for general
application. To achieve the design, the mix proportion of normal
grade concrete consists of cement less than 380 kg/m3, normal
type of aggregates which is normally granite, medium water
requirement and little dosage of superplasticizers [3]. Eventually,
starting from 1960, when unique design of structure was created
and most of the structure carries load more than 50 MPa up to
95 MPa [4,5]. Since then, a new technology for concrete was cre-
ated like High Strength Concrete (HSC). HSC can withstand load
capacity from 50 MPa until 90 MPa [6,7]. Prior to that, it can be
seen that concrete has been utilised for high rise building, bridges
and heavy load structures. In terms of mix proportion, HSC
requires more cement, high content of aggregates, less water and
adequate superplasticizer. To realise this, additives and supple-
mentary materials such as silica fume, fly ash, metakaolin and
other pozzolanic were implemented [810]. Silica fume was popu-
lar in HSC mix due to its ability to increase strength at adequate
percentage of cement replacement [1014]. In contrary, fly ash
(FA) addition in HSC mix increases flow ability and also act as nat-
ural admixture. Other advantages of using FA in HSC mix is, FA can
be an alternative to superplasticizer because it can be replaced at
higher dosage and is cost effective [1518]. Metakaolin (MK) as
cement replacement material has started since early 90s [19
23]. Metakaolin is a secondary product of kaolin after undergone
heat treatment. The unique feature of MK is it is clay based and
allows low water penetration into concrete. Table 1 tabulated the
different mix proportion between normal concrete, high strength
concrete with silica fume inclusion and UHPC mix used in other
studies. Obviously an increase in cement component is seen from
those three different concretes. Furthermore, other properties
which include aggregates, admixture, water to cement ration and
slump are also different.
2. Development of nano concrete
Nano concrete is a concrete that utilises nano materials or a
concrete with nano materials added in which the size of the nano
particles is less than 500 nm [6,2631]. It was believed that the
addition of nano particles in concrete improve the strength of con-
ventional concrete. Nano particle works in concrete by improving
the bulk properties or also known as packing model structure.
Ultra or nano particles can perform a superb filler effect by refining
the intersectional zone in cement and producing more density con-
crete. By acting as good filler, their manipulation or alteration in
the cement matrix system occurs to provide a new nanoscale
structure. Common discrepancies in concrete microstructure such
as micro void, porosity and deterioration due to alkali silica reac-
tion will be eliminated. Next, nano materials start to evolve when
they become new binding agent which is smaller than cement par-
ticles. This improves the structure of hydration gel providing a neat
and solid hydration structure. In addition, through the combina-
tion of filler and additional chemical reaction in hydration system,
Table 1
A summary of concrete properties for different types of concrete obtained from past researchers.
Compressive strength (MPa)
Normal concrete 1040
High performance concrete (HPC) 41100
Ultra high performance concrete (UHPC) 100
Nano concrete 70
a new concrete called nano concrete with durable and enhanced
performance has been developed [5,32,33].
Implementation of nano technology in concrete has started
since the early millennium in line with the increasing demand
for UHPC. Conventional mix formulations of UHPC with the inclu-
sion of silica fumes provide better durability and strength. How-
ever, due to limited availability and also the high cost of silica
fume makes UHPC technology declining and less demanding com-
pared to HSC. Since then, emerging technology in nano production
has developed an alternative to silica fume. By applying nano pro-
duction concept, a common nano material which mimics the action
of silica fume is designed. Nano silica is one of the newest tech-
nologies in nano process which has been used as an alternative
to silica fume [34]. Since the breakthrough of nano silica, many
nano based particles has been developed to be used in concrete.
Nano alumina [35], titanium oxide [36], carbon nano tube [37]
and polycarboxylates [38] are examples of nano materials used
in nano concrete. The following sub-section explains on the
production and application of nano materials.
3. Production of nano materials
Since the emergence of nano technology in the late 60s, the
idea and concept of producing nano materials have also been
developed. The nano size in nano particles produces a greater
effect on filler as compared to micro based materials. Guterrez
[39] reported that all materials can be transformed into nano par-
ticles. The success of nano particle formation is when it can influ-
ence the purity or basic chemical composition of parent materials.
From that, two methods were developed. The first is top to down
approach [40] and the second is bottom to up approach [41]. Selec-
tion of those two methods is based on suitability, cost and exper-
tise of nano behaviour [2,24,25]. One of the technique for top to
down approach is using milling. The selection of milling technique
is due to the availability of the milling machine and its feasibility
as any modification can be applied directly without any chemical
or electronic devices needed. The definition of top to down
approach is, larger structures are reduced in size to nanoscale
while maintaining their original properties or chemical composi-
tion without any alteration on atomic level control [1,42]. In other
words, bulk materials are broken down into nano particles by
mechanical attrition and etching techniques. This method is uti-
lised in massive industries. Nano particles produced are in high
volume using milling technique since is cost effective and easy to
be maintained as it involves more mechanical instruments and less
chemical alteration. Another term used to describe top to down
approach is contemporary method in nano fabrication. However,
uniformity and quality of the final product are inconsistent in
top to down approach. Although there are disadvantages in top
to down approach, with modification on milling techniques which
includes numbers of ball, types of ball, speed of milling and types
of jar used, the quality of nano particles can be improved
[40,43,44]. High energy ball millings are widely exploited in syn-
thesising nano particles which involves nanomaterials, nanograins,
nanoalloy, nanocomposites and nano quasicrystalline materials.
The pioneer of milling technique was John Benjamin in producing
Flexural strength (MPa) Porosity (%) Water absorption (%) Remark
110 <30 <30 Mehta and Monteiro [3]
1120 1225 1225 Hamid, Yusof [49], [50,51]
2030 <10 <12 Hartmann [52], [53,54]
1220 <10 <12 Atcin [26], Chong [28]
 M.S.M. Norhasri et al. / Construction and Building Materials 133 (2017) 9197
oxide particles in nickel superalloys (1970). His first attempt using
milling was when he altered and strengthened alloy component for
application in high thermal structure [45]. During milling, plastic
deformation, cold welding and fracture are the factors influencing
the deformation and transforming process of materials into
required shape. Milling does not only breaking materials into smal-
ler parts but also blending several particles or materials and trans-
forming them into new phases of material composition. Normally,
the final product of milling technique is flakes in shape but refine-
ment can be done depending on the selection of ball and type of
milling. However, most of nano materials such as nano silica, nano
alumina, nano clay which were used in concrete are produced by
using bottom to up approach. Bottom to up approach is adopted
when materials are engineered from atoms or molecular compo-
nents through a process of assembly or self-assembly. It also
known as molecular nanotechnology or molecular manufacturing
process which involves more indirect applications such as synthe-
sis and chemical formulation [24]. Nano particle size and shape
created by using bottom to up approach can be designed and con-
trolled using chemical synthesis technique. The difference in this
method as compared to top to down is the bottom to up approach
will produce more uniform and neat structure of nano particles. In
other words, bottom to up also produces new nanocrystals because
the atom or molecules are perfectly ordered or crystalline. The
techniques involved are electronic conductivity, optical absorption
and chemical reactivity [25,46]. By using bottom to up technique,
reduction in size and neat surface atom formation can be achieved
and imparts a huge change in surface energies and morphologies.
Normally, by using this technique, application of nanomaterials
can be widely adapted in conditions such as improving in catalytic
capability, sensing wave ability, new pigments and paint with self-
healing and cleaning features. However, the disadvantage of bot-
tom to up approach is its expensive operational cost, expertise
requirement in chemical applications and limited suitability as it
meant for laboratory only [39,47,48]. However, nanoparticles har-
vested using this method is also best for advance applications such
as in electronic component and biotechnology.
As a conclusion, apart from evaluating the effects of nano mate-
rials, two (2) different approaches of producing kaolin as nano
materials to be utilised in UHPC were also discussed. Thus, it is evi-
dent that there are two different methods of producing nano mate-
rials in developing new UHPC.
4. Application of nano materials in UHPC
Since the breakthrough of nanotechnology in the field of con-
struction, various nano materials have been adopted in concrete.
As mentioned in earlier sections, improvement in enhancing per-
formance and durability of concrete can be achieved by using nano
materials. In this sub sections, discussion on the nano materials
reported by previous researchers and its use in UHPC will be fur-
ther elaborated.
5. Nano silica
Nano silica is a breakthrough in nanomaterials that has been
applied in UHPC. In general, nano silica was produced from micro
based silica. The positive reactions created by nano silica in UHPC
are similar to silica fume or micro silica which are in terms of per-
formance strength and durability enhancement [5557]. Studies
by Qing, Zenan [56], showed that concrete with addition of nano
silica gained early strength as compared to that of silica fume. It
was also revealed that the addition of nano silica in concrete
improved workability of concrete while the addition of superplas-
ticizers is at a minimum dosage. The reason behind the workability
93
improvement is the round shape of nano silica which provides a
ball bearing manoeuvre in cement particles. Furthermore, size of
nano silica which in nano particles acts as ultra-filler in concrete.
Micro voids in concrete will be densified and refined to provide
neat concrete microstructure [58,59]. Other advantages of nano sil-
ica are the water to cement ratio can be controlled and targeted
strength can be modified easily with controlled dosage. Another
report by Quercia. G, Hsken. G [60] revealed that the addition of
nano silica at certain dosage just not improved strength of HSC
but also acted as cement replacement material. About 20%30%
of cement content can be reduced by nano silica. Thus, nano silica
can be an alternative material to cement. However, the disadvan-
tage of nano silica is its price and availability in certain countries.
Some countries have to import nano silica to be used in concrete
industry [4].
6. Nano alumina
Silica and alumina are two (2) major chemicals involves in
cement hydration. The function of silica in cement is to change
strength properties where alumina controls the setting time of
cement. Nano alumina is formed from alumina itself. There are
limited studies reported on the use of nano alumina in concrete.
The addition of nano alumina in concrete especially UHPC can
hugely affect concrete properties as it controls the setting time of
cement. The function of nano alumina in cement is to speed up
the initial setting time for UHPC. This will reduce segregation
and flocculation. Disruption in cement will create non homogene-
ity in UHPC mixes, and hence the performance of UHPC will be
affected. Nano alumina in UHPC acts as dispersion agent in cement
particles [6164]. Furthermore, since the size is in nano form, nano
alumina also refines the voids in the hydration gel as nano filler.
Since cement content in existing UHPC proportion is high, disper-
sion of cement grains in UHPC must take place concurrently with
silica action in the hydration process. Without nano alumina refin-
ing of hydration product, the hydration process will be slower
because the internal structure of hydration gel cannot be pene-
trated by silica component. By adding nano alumina, the path will
be created and silica or binding materials will be easily injected
into the microstructure of hydration gel and the refining process
will start [27,62,65].
7. Carbon nano tube (CNT)
Carbon nanotube (CNT) is allotropes of carbon with a cylindrical
nanostructure. Nanotubes have been constructed with length-to-
diameter ratio of up to 132,000,000:1, significantly larger than
any other material. These cylindrical carbon molecules have unu-
sual properties, which are valuable for nanotechnology, electron-
ics, optics and other fields of materials science and technology
[1,39,66]. In particular, owing to their extraordinary thermal con-
ductivity and mechanical and electrical properties, carbon nan-
otubes find applications as additives to various structural
materials.
Nanotubes are members of the fullerene structural family. Their
name is derived from their long, hollow structure with the walls
formed by one-atom-thick sheets of carbon, called graphene. These
sheets are rolled at specific and discrete angles, and the combina-
tion of the rolling angle and radius decides the nanotube properties
[37]. Nanotubes are categorised as single-walled nanotube (SWNT)
and multi-walled nanotube (MWNT). Individual nanotubes natu-
rally align themselves into ropes held together by van der Waals
forces or more specifically pi-stacking [67,68]. Those so called
ropes in CNT structure are chemically bonded in CNT structure.
The chemical bonding of nanotubes is composed similar to those
94 M.S.M. Norhasri et al. / Construction and Building Materials 133 (2017) 9197

of graphite. These bonds, which are stronger than the bonds found strength of HSC at early age. It was reported that at day one, the
in alkanes and diamond, provide nanotubes with their unique strength of HSC can go from 40 to 80 MPa. At 28 days, strength
strength. can be achieved at around 70100 MPa easily at lower dosage of
The advantage of using CNT in UHPC is its flexibility. From this, PCE. This proves that PCE can be an alternative admixture to
the design of UHPC can be altered into either unique or rigid enhance the strength of concrete. Due to its easy handling charac-
design. Flexibility provided by CNT also increases the strength of teristics with minimum guideline or technique required, makes
UHPC. As compared to other nano materials, CNT is the best nano PCE one of the most popular nano materials to be adopted in UHPC.
material in terms of improving flexibility and enhancing strength
of UHPC [37]. Most of all, volume and size of CNT are smaller as
9. Titanium oxide
compared to other nano materials. The main reaction of CNT in
UHPC is to improve the tension and compression abilities [69].
Titanium oxide (TiO2) is also known as titania, is the naturally
Steel reinforcement section can be replaced by CNT which permits
occurring oxide of titanium. The chemical formula for titania is
extra loads to be handled. By replacing steel in UHPC, it was
TiO2. When used as a pigment, it is called titanium white. Gener-
believed that more lightweight and less reinforcement sections
ally, it is sourced from ilmenite, rutile and anatase. It has a wide
can be created. In addition, time and the cost of construction can
range of applications, from paint to sunscreen to food colouring.
be reduced. However, lack of CNT sources reduces the interest of
Titanium dioxide occurs in nature as well-known minerals rutile,
having CNT in UHPC. Being extremely pricy, having less expertise
anatase and brookite. Additionally, titanium is also formed from
and limited guidelines in it preparation are some of the factors that
two (2) high pressures called monoclinic baddeleyite-like form
makes CNT not unsuitable for UHPC mix.
and an orthorhombic form, both found recently at the Ries crater
in Bavaria [67,72]. It is mainly sourced from ilmenite ore. This is
the most widespread form of titanium dioxide-bearing ore around
8. Polycarboxylates
the world. Rutile is the next most abundant and contains around
98% titanium dioxide in the ore. The metastable anatase and broo-
Polycarboxylates is one of the nano materials that has been
kite phases convert after heated above temperatures in the range
used in concrete [70]. In general, polycarboxylates (PCE) is a poly-
600-800 C [25,73].
mer based composed by methoxy-polyethylene glycol copolymer
Normally, the addition of TiO2 in UHPC and concrete has proven
acts as secondary or side reaction that is reinforced with
a great effect on self-cleaning ability and contribute to the applica-
methacrylic acid copolymer which acts as the main component.
tion of green material in construction [74]. Self-cleaning effect of
The carboxylate group normally consists of water particle, provid-
TiO2 has been utilised in buildings, paving material and the finish
ing a negative charge along the PCE backbone. The polyethylene
product can be seen on the construction of Jubilee Church in Rome
oxide group offers a non uniform distribution of electron cloud,
Italy [25]. Another benefit of TiO2 is accelerating strength of con-
which gives a chemical polarity to the secondary or side reaction.
crete at early age. Furthermore, performance of concrete also
The number and the length of secondary or side reactions are flex-
improves and abrasion resistance in concrete increases [75]. Basi-
ible parameters that are easy to change. When the secondary or
cally, those effects are provided by TiO2 in UHPC and concrete
side reactions have a huge amount of electron units, they lower
due to TiO2 is ability to act as glass layer or pigment outside the
their high molar mass and change the density of the polymer,
concrete particles and also in the microstructure of UHPC and con-
which results in poor performance on cement suspensions. In order
crete. Those layers react to the hydration gel during mixing and act
for both chains to merge and paired at the same time, long side
as protective layer that gives self-cleaning ability to the concrete
particles and high charge density must be connected from one to
surface. The self-cleaning effect provided by TiO2 surrounds the
another reaction.
outer surface concrete and coats concrete surface which is hard
Normally, polycarboxylate is applied in concrete as high range
and permeable. For enhancement in performance, TiO2 in concrete
water reducer (HRWR). The addition of PCE will help to control
forms a fiber reinforced system which can be seen mimicking the
the workability of concrete at low water to cement ratio. The prop-
glass fiber effect. Refining and tailoring the hydration gel by acting
erties of PCE in concrete depend on the dosage of PCE. Too high
as fiber contribute to the strength enhancement and more durable
dosage will result in false set or no hydration occurrence in con-
concrete [76].
crete [71]. Apart from that, inclusion of PCE at required dosage will
However, issues on safety and health were among the problems
produce Self Compacting Concrete (SCC). SCC increases the worka-
arised in TiO2. Although there is no report on the pollution but par-
bility of concrete and produces a flow concrete which gives great
ticles of TiO2 which are dusty and small create the environmental
impact during the placing of concrete at low and high intensity
effect to factory workers during packing and production. It was
area. Another advantage of having PCE in UHPC or concrete is its
believed that titanium creates inflammatory effect and danger-
ability to be used in marine structure. Since PCE has the ability
ously causing cancer to factory workers [75]. Therefore, care during
to remove air bubble in improving density of concrete, pores or
handling must be taken seriously which includes mixing process of
voids in UHPC will be reduced to provide a compact structure. In
TiO2.
addition, refining of UHPC microstructure will prevent or reduce
the rate of permeability when dealing with marine condition. From
that, the attacks of sea water such as sulphate and chloride content 10. Nano kaolin
can be controlled or reduced. Besides, the use of polycarboxylate is
considered as a greener technique compared to silica fume and any Nano kaolin is a by-product of kaolin. Kaolin or its chemical
additives in refining microstructure of UHPC. Sobolev (2005) name, kaolinite is a clay mineral, part of the industrial minerals,
reported that utilisation of PCE in HSC enhances workability and with the chemical composition Al2Si2O5(OH)4. It is a layered sili-
performance compared to that of silica fume. Furthermore, almost cate mineral, with one tetrahedral sheet linked through oxygen
70% of depending material in UHPC such as silica fume, superplas- atoms to one octahedral sheet of alumina octahedral [77,78]. Rocks
ticizers and fibers can be reduced [2,32]. Finally, the study showed that are rich in kaolinite are known as kaolin or china clay [79].
that PCE in UHPC enhances the strength performance as compared Kaolinite contains white mineral that is also known as dioctahe-
to those of plain UHPC or HSC. Crainic (2002) reported that PCE dral phyllosilicate clay. It is formed from clay which is produced by
inclusion at around 2.5% of cement weight rapidly increases chemical weathering of aluminium silicate minerals such as feld-
 M.S.M. Norhasri et al. / Construction and Building Materials 133 (2017) 9197
spar [77,80]. The chemical formula for kaolinite as used in miner-
alogy is Al2Si2O5(OH)4. However, in ceramic applications, the for-
mula is typically written in terms of oxides, which after being
treated by heat treatment change into Al2O3
2SiO2
2H2O. Further-
more, kaolin after treatment or endothermic dehydration will
change from crystal to amorphous stage [81]. The transformation
will change it into new formation of clay called metakaolin. Meta-
kaolin consists of amorphous silica and alumina, and the structure
is in long order or hexagonal layers [79,82]. Metakaolin has been
known as very reactive pozzolan and performs similar reaction to
silica fume. Strength enhancement and improved durability by
refining microstructure, allowing reliable water penetration and
making cost effective are the stronger points in metakaolin as com-
pared to silica fume [19,20,8385].
Nano kaolin is formed using either top to down or bottom to up
approach. Those processes will influence the final formation of
nano kaolin. Generally, the basic but major formation of nano kao-
lin involves layering or stacking flakes. At a glance, the particle of
kaolin is similar to nano kaolin. Morphological properties of kaolin
after the transformation in size from micro to nano is its particles
provide larger surface area. In concrete, nano kaolin must undergo
treatment in order to form a more reactive or stable component;
nano metakaolin. Nano metakaolin is still newly used as supple-
mentary in concrete, but the enhancement in concrete properties
is expected, due to the positive impact of metakaolin in UHPC
and other types of concrete. In a report by Morsy et al. [86], nano
metakaolin addition in concrete has improved the strength of mor-
tar where almost 8%10% increment of compressive strength can
be achieved. The most interesting finding is, tensile and flexural
enhancement of mortar containing nano metakaolin is around
10%15% as compared to plain OPC [86,87].
Although the earlier discussion shows the advantages of nano
metakaolin inclusion in improving performance of mortar, there
are still limited resources on the application of nano metakaolin
in UHPC. Lack of raw kaolin in certain countries makes nano meta-
kaolin unpopular as compared to silica fume. Therefore, guidelines
and commercial technique in producing nano kaolin and nano
metakaolin need to be exposed and intensive research has to con-
tinue in order to maximise its potential as nano material alterna-
tive in concrete.
11. Nano clay
Nano clay is nanoparticles of layered mineral silicates. Depend-
ing on the chemical composition and nanoparticle morphology,
nanoclays are organised into several classes such as montmoril-
lonite, bentonite, kaolinite, hectorite, and halloysite. Nanoclay is
one of the most affordable materials that have shown promising
results in polymers. Nanoclay is made of montmorillonite mineral
deposits known to have platelet structure with average dimen-
sion of 1 nm thick and 70150 nm wide. The unique structure of
montmorillonite clay is it possesses several qualities that make it
an excellent base for manipulation through nanotechnology. These
qualities include stability, an interlayer space, high hydration and
swelling capacity and a high chemical reactivity.
Characterisation of clays and their modified organic derivatives
can be characterised using simple as well as modern tools which
include determination of chemical compositions by gravimetric
analysis, inductively coupled plasma (ICP) or XRF, cation exchange
capacity (CEC) using standard ammonium acetate method, surface
area measurement, Fourier transform infrared spectroscopy (FT-
IR), powdered X-ray diffraction (PXRD) and others [58,8890].
The clays are also characterised by their cation exchange capaci-
ties, which can vary widely depending on the source and type of
clay. The purity of the clay can affect the final nanocomposite prop-
95
erties. Due to this, it is very important to have montmorillonite
with minimum impurities of crystalline silica (quartz), amorphous
silica, calcite and kaolin [77,88]. The technique mainly used for
purification of clays includes hydrocyclone, centrifugation, sedi-
mentation method and chemical treatment [78,82].
Clays can be considered as inexpensive materials. Having nano
materials from clay based can be adaptable with adequate cost.
Despite the occurrence of clay in most parts of the world, guideline
and techniques to imply and form clay to nano materials is still
unrevealed. Research on the advantages and disadvantages of nano
clay as construction materials need to be explored. Nano clay has
been widely used in polymeric system. However, the evidence on
improvement and enhancement in material stiffness, thermal sta-
bility, as barrier coating, solvents and other improvement espe-
cially in electronic and new form of materials are needed.
Normally in construction, nano clay is applied as an additive to
enhance concrete properties. Morsy et al. [86] reported that,
enhancement in compressive and tensile strength for mortar
cement having nano clay as additive was recorded. Thermal beha-
viour of concrete also improved after nano clay was added as
cement additive in paste [91,92].
12. Summary
From the review of the existing literature, it is clear that the use
of nano materials in concrete is beneficial in improving some tech-
nical properties of cement based materials although it deficients in
some properties for example on water demand. In this review also,
utilisation of nano materials in concrete is reported. Nano silica,
alumina and titanium oxide are among the nano materials used
in the current research in developing the nano based concrete.
The addition of nano materials in concrete has similar effect to
the effect of micro based materials such as metakolin and silica
fume. Pore refinement and increased strength and durability of
concrete are expected. The only different is the size of the materials
is deduced to nano scale. Since in micro based materials, enhance-
ment of concrete in strength and durability is proven, when using
nano particles, concrete properties are likely to be improved. Till
now the inclusion of nano metakaolin and nano metaclay in con-
crete has not been revealed and this is the reason for pursuing
for further investigations. Based on the literature, metakaolin as
cement replacement material in UHPC provides a similar effect to
the silica fume in improving the properties of concrete.
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