FACULTY OF ENGINEERING, TECHNOLOGY AND BUILT

ENVIRONMENT

EP 431 NANOTECHNOLOGY
JAN – APR 2020

ASSIGNMENT 2

TITLE: CARBON NANOTUBE AS FILLER TO ENHANCE THE PROPERTIES OF

CONCRETE/CEMENT

GROUP MEMBERS : ANG SHEN JEN (1001643371)

BILL LEE YOON HO (1001644191)
DING SHUAN WEI (1001540160)
AINGGARARUBAN GANESHAN (1001642979)
NICHOLAS DAWSON (1001643608)
LIEW SHU QING

LECTURER : DR YEAP SWEE PIN

DATE OF SUBMISSION : 27TH MARCH 2020

 CHAPTER 1: CHEMICAL STRUCTURE AND UNIQUE PROPERTIES OF
CARBON NANOTUBE

1.1 Chemical Structure

Carbon nanotube (CNT) is a type of carbon, having a diameter of nanometer and a

length of micrometer (where the length to diameter ratio exceeds 1000). The atoms are
arranged in hexagons, the same arrangement as in graphite. CNT's structure consists of
enrolled cylindrical graphite sheet (called graphene) rolled up into a seamless cylinder with
the size of a nanometer in diameter. It is stated that CNT is the material lying in between
fullerenes and graphite as a quite new member of carbon allotropes (Tanaka et al, 1999).

1.1.1 Single walled carbon nanotube

The rolling of a single layer of graphite (graphene layer) can be known as a single
walled carbon nanotube (SWCNT) and it forms a seamless cylinder. Single Walled Carbon
Nanotubes are classified as one-dimensional, cylindrically shaped carbon allotropes with a
high area and aspect ratio (length to diameter). SWCNTs are so named because of their
hollow structure and number of walls. They’re made of one-atom-thick nanocarbon sheets
that forms a tube shape during synthesis and are members of the fullerene family. A "zigzag"
path on a graphene-like lattice as a path which turns 60 degrees, alternating between left and
right, following each bond and it is shown in figure 1.2. It is also popular to describe an
"armchair" path as one that makes two 60-degree left turns followed by two right turns every
four steps and is shown in figure 1.3.
FIGURE 1.1 Single walled carbon nanotube.

FIGURE 1.2 Zig-zag configuration.

FIGURE 1.3 Armchair configuration.

1.1.2 Multiple walled carbon nanotube

Multi-walled nanotubes (MWNTs) consist of multiple rolled layers (concentric tubes)

of graphene. Double-walled carbon nanotubes (DWNTs) form a special class of nanotubes
because their morphology and properties are similar to those of SWNTs but they are more
resistant to chemicals. The name derives from their construction, and the walls are formed by
several carbon sheets of one atom thickness. MWNTs consist of several rolled layers of
condensed graphene nanotubes inside other nanotubes.

In MWCNTs the interlayer gap is similar to the gap in graphite between graphene
layers, around 3.3 Å (Aqel, El-nour, Ammar, & Al-warthan, 2012). The special case of
MWCNTs (double-walled carbon nanotubes DWCNTs) needs to be illustrated here because
they combine morphology and properties very similar to SWCNT (Flahaut et al., 2003)

FIGURE 1.4 Multiple walled carbon nanotube.

1.2 Unique Properties

1.2.1 Electrical conductivity

CNTs with different combinations of N and M (structural parameters showing how

twisted the nanotube is) can be extremely conductive and can therefore be assumed to be
metallic. It has been shown that their conductivity is a function of their chirality (degree of
twist), as well as their diameter. In their electrical activity CNTs can be either metallic or
semi-conductive. SWCNTs are a very valuable variety of a CNT because they possess
valuable electrical properties that the MWCNT variants do not share. The electric wire is the
most fundamental building block of these systems and SWCNTs can be excellent conductors
(Aqel A. et al ,. 2010).

MWNT conductivity is relatively complex. Several forms of "armchair "- structured

CNTs tend to be conducting better than other metallic CNTs. In addition, interwall reactions
within MWNTs were found to non-uniformly redistribute the current across individual tubes.
Nevertheless, there is no difference in current through various sections of single-walled
metallic CNTs.

1.2.2 Strength and elasticity

Carbon nanotubes have a greater resistance to tensile than steel and Kevlar. Its power
comes from the bonds between the carbon atoms of individual sp2. This bond is much more
effective than the diamond bond found in sp3. Individual nanotubes will bind together under
high pressure, exchanging some sp2 bonds for sp3 bonds. This gives long nanotube wires the
opportunity to be made (Scoville, Cole, Hogg, Farooque, & Russell, 1991). Thanks to these
tight bonds, the graphite elastic basal-plane modulus is one of the highest of any known
substance. CNTs are considered to be the ultimate high resistance fibres for this purpose.
SWNTs are more durable than steel and are highly resistant to physical force injury. Clicking
on a nanotube's tip can cause it to bend but without damage to the surface. After withdrawal
of power, the tip returns to its original location. This property makes CNTs very useful as
probe tips for very high-resolution scanning probe microscopy.
1.2.3 Thermal conductivity and expansion

The strong graphic C-C bonds in-plane make them extremely solid and rigid against
axial stresses. The thermal expansion of SWNTs nearly zero in-plane but large inter-plane
expansion implies good in-plane coupling and high flexibility against nonaxial stresses. The
strength of the carbon nanotubes atomic bonds allows them to withstand the high
temperatures. Because of this it has been shown that carbon nanotubes are very strong
thermal conductors. The carbon nanotubes can transmit more than 15 times the number of
watts per meter per Kelvin as compared to copper wires which are widely used as thermal
conductors. The thermal conductivity of carbon nanotubes depends on the thermal of the
tubes and the external environment (Tomanek, 2013).

1.2.4 Electron emission

Energy emissions are the result of tunnelling the electrons from a metal tip into the
vacuum, using a strong electric energy. The small diameter and high aspect ratio of CNTs for
field emission is very favourable. Also, for moderate voltages, due to their sharpness a heavy
electrical field emerges at the free end of the assisted CNTs. This luminescence is induced by
the electron field emission, since it is not detected without applied potential. This light
emission occurs in the visible part of the spectrum, and can sometimes be seen with the naked
eye (Y. Cheng et al., 2003).

1.2.5 High aspect ratio

CNTs are a very low, high aspect ratio conductive additive to all forms of plastics.
Their high aspect ratio means that in order to achieve the same electrical conductivity a lower
charge (concentration) of CNTs is necessary compared to other conductive additives. This
low charge preserves more of the durability of the polymer resins, particularly at low
temperatures, as well as preserving other main performance properties of the matrix resin.
CNTs have proved to be an excellent additive in plastics for imparting electrical conductivity.
Similar to traditional additive materials like carbon black, chopped carbon fibre, or stainless
steel fibre, their high aspect ratio (about 1000:1) imparts electrical conductivity at lower
loadings (Dervishi, et al., 2010).
CHAPTER 2: EFFECT SOF PARTICLE SIZE AND SHAPE ON THE UNIQUE
PROPERTIES OF THE NANOPARTICLE
TABLE 2.1 Effects of Shape on the unique properties of Carbon Nanotube
Shape
Single Walled Carbon Nanotube
Multi-Walled Carbon Nanotube
Double-Walled Carbon Nanotube
Properties
 Has high electronic nature due to its
ballistic nature for transporting
electron.
 Has young-modulus that is as high as
diamond which mainly depends on
the CNT diameter.
 Estimated if the diameter is more than
1 nm then it will have the range of
0.6-0.7 TPa.
 Has resistivities ranging from 0.34
x10-4 to 1 x10-4
 Has 200 W/K of thermal
conductivity at room temperature
 Similar properties to single wall
nanotube but more chemical resistant.
 Zero-Gap Metal
 Only outer layer of nanotube is
modified
 Has higher strength than single-
walled CNT
 Not easily twisted
 High structure complexity
 High purity
 Has 3000W/K of thermal
conductivity at room temperature.
 Has high field emission properties

(Single) Armchair Carbon Nanotube
(Single) Zig Zag Carbon Nanotube
(Single) Chiral Nanotube with Beads
 High transparency
 Intermediate properties between
single and multi-wall CNT.
 Has Raman and optical characteristic
of each wall
 High stability when exposed to
aggressive chemicals
 Has electrical properties that are very
similar to metals that allow
voltage/current to flow between the
nanotube.
 Better conductor than metals
 Metallic
 Conduct electric current when there is
an extra energy from a form of light
or when there is an electrical field
applied to the free electron of the
carbon nanotube
 Can be metallic or semiconducting
 Same properties with Zig-Zag Carbon
Nanotube.
 Conduct electric current when there is
 an extra energy from a form of light
or when there is an electrical field
applied to the free electron of the
carbon nanotube
 Can be metallic or semiconducting

Beaded Carbon Nanotube

 High viscosity of carbon on the
nanotube surface
 Used as filler to improve electrical
and mechanical conductivity.

Coiled Carbon Nanotube

 Has high efficiency of

electromagnetic wave capacity

TABLE 2.2 Effects of Particle Size on the unique properties of Carbon Nanotube

Properties Particle Size Effects

Mechanical  Lower the particle size higher the surface area
 of grain boundaries per unit volume increase
hence hardness is increase
 Lower the particle size higher the surface area
of grain boundaries per unit volume increase
hence ductility is increase
 With the decrease of particle size, there are
more defect hence lower the elasticity due to
difficulties of atom to return to original
Physical position
 Bigger the particle size, with more atom it has,
the higher the bond energy hence higher
melting point due to higher cohesive energy.
 Higher the particle size, the higher the
Magnetic
magnetophoresis of the particle.
 Smaller the particle size, higher the surface
Electrical
area hence they are able to hold more energy.
 Higher the particle size, the increased of
Optical scattering and has higher peak at longer
wavelength
 Lower the particle size, higher the grain
boundary surface area. Then it will have better
Thermal
phonon scattering hence better thermal
conductivtities

CHAPTER 3: APPLICATION OF CARBON NANOTUBE AS FILLER TO

ENHANCE PROPERTIES OF CONCRETE/ CEMENT

3.1 Working Principle/ Mechanism

 Because of all the excellent properties of carbon nanotubes as discussed above, it has
a wide range of application in many different sectors and aspects. It usage is particularly
prominent in the following sectors: energy, medical, environmental, electronics and
construction. One of the main usage of CNT is in the construction industry. CNT are widely
used as cementitious fillings for concrete and cements which are used to construct buildings.
Researchers have found that carbon nanotubes can fill the voids that occur in conventional
concrete. These voids allow water to penetrate concrete causing cracks, but including
nanotubes in the mix the cracking can be stopped.

The CNTs and cementitious matrixes bond together by means of two main methods,
that being the formation of covalent bonds between functional groups of the CNT surfaces
and hydration products of the cement matrix as well as with the addition of surfactants and
admixtures, which brings about a physical reaction between the CNT and cement instead of
covalent interfacial bonding. The first strategy, which occurs naturally, involves the reaction
between a carboxylic acid (-COOH) group on the surface of a CNT and a C-S-H cement
product. The mechanism is briefly illustrated in Figure 3 below. (Fraga, María, & García,
2014)

FIGURE 3.1 Reaction scheme between carboxylated nanotubes and cement hydration
products (Ca(OH)2 and C-S-H)
3.2 Advantages and Disadvantages of Carbon Nanotube

3.2.1 Advantages

Carbon nanotubes (CNT) possess a high modulus of elasticity, tensile strength and
yield strain. They have a modulus of elasticity in the range of Terra Pascal and tensile
strength up to an order of Giga Pascal. In fact, CNT are among the strongest and stiffest
material in terms of tensile strength and elastic modulus, which is mainly attributed to the
presence of carbon–carbon sp2 bonding. These properties make CNTs an attractive
reinforcing material for concretes. These unique properties and features that are offered by
CNTs provide an excellent opportunity to develop CNTs reinforced structural concrete. By
adding CNTs to the concrete mix will improve the cement compositions in tension due to its
ability to prevent the initiation of micro cracks in cement mix. Besides that, other beneficial
effects of CNTs on the microstructure and properties of cement nanocomposites are that it
helps a properly dispersed nanoparticle from crystalline centre and speeds up the cement
hydration process. Next, the carbon nanotubes nanoparticles will fill up the free spaces
between the grains and prevent any flow of water in between them. It contributes the
production of small crystals such as calcium hydroxide, Ca(OH)2 and provides a uniform
agglomeration of calcium silicate hydrate (C-S-H) products that primarily responsible for the
strength in cement based materials. CNTs also help accelerate pozzolanic reactions, which
helps to consume the calcium hydroxide and produce additional C-S-H gel. Lastly, CNTs
enhances the contact zone of the cement, which increases bonding strength between cement
compound and aggregates.

3.2.2 Disadvantages

Carbon nanotubes, CNTs as reinforcement for cementitious composites have multiple

cons. First of all, carbon nanotubes in general are extremely small hence it is difficult to work
and comply with. It is also relatively expensive for the process to produce nanotubes. It will
be expensive to implement this new technology in and to replace the older technology in all
the places that we could. At the rate of the current technology becoming obsolete, it may be a
huge risk or gamble to bet on this technology. Carbon nanotubes may also cause a possible
environmental risk. Next, the strong Van der Waal’s force between CNTs make it difficult to
disperse them homogenously. This force is strong due to the surface to volume (SA/V) ratio.
It tends to attract agglomerate and sediment. Next, the hydrophobicity of CNTs will lead to a
weaker bonding of CNTs to the cement matrix.
3.3 Improvements of Concrete/Cement upon usage of CNT

Advance technology aspects on cement-based composites have been put to focus

recently on developing a newer and better materials that are higher in performance and has
high compressive strength. However, cement composite currently exhibits a low tensile
capacity and extremely brittle failure properties. They are sensitive to an early age of
microcracking as a result of volumetric change due to high autogenous shrinkage stresses.

Hence, a bigger effort is rise to tailor the tensile and flexural material mechanical
properties of the cement in order to improve the fracture and damage resistance of the
concrete cement. Nanoparticle materials provides a unique multifunction property due to its
nanoscale. Carbon nanotubes are the most promising material to be used as a filler to improve
concrete nanocomposites properties. Single-walled carbon nanotubes (SWCNTs) are widely
used because it is cheaper to manufacture and offers better reinforcement in cement
composites.

With the application of carbon nanotubes onto cements, cement composites have a
proper dispersion in water and subsequently in cement paste. It has a higher compressive
strength as well as the flexural strength comparing to the normal compressive and flexural
strength from a plain cement composite. Next, the CNTs-cement composite has an obvious
improvement in the microstructure of the composites where the smaller size of CNTs act as a
filler and therefore the bonding between the hydration product and surface of the CNTs is
improved. Hence, the composite will experience a lower porosity which leads to a delay in
micro cracks initiation.

Apart from the strength characteristics, CNT also contributes to the betterment of
concrete/cement in several other ways. For instance, improvement of mechanical
performance, resistance to chloride penetration as well as self-compacting properties of
concrete. Apart from that CNT also greatly reduces the permeability and shrinkage. The most
important application of nanotubes based on their mechanical properties will be as
reinforcements in composite materials. Makar et al. were among the first few people to
discover that by using hardness measurements, that CNTs can affect early-age hydration and
subsequently a strong bond will be formed between the CNT and the particles of the
concrete/cement.

CHAPTER 4: NANOTOXICITY OF CARBON NANOTUBE

 Carbon nanotubes can be classified into two types, which are single walled carbon
nanotubes and multiple walled carbon nanotubes. Regardless, both carbon nanotubes types
are used in various biomedical devices and therapies due to their unique properties. A few
common properties of carbon nanotubes include chemical stability, light weight, the ability to
deliver drugs in a cellular environment, and the ability to absorb near-infra-red light and
generate heat. Due to their medical applications. Carbon nanotubes can enter human body
through ingestion, inhalation, injection and skin penetration.

Despite the contribution of this nanoparticles in biomedical industries, the

nanotoxicity still remain as one of the researchers’ concern. According to Lam, James,
McCluskey, & Hunter (2003), the nanotoxicity of carbon nanotubes was tested on mice. It
was discovered that the nanoparticles has triggered epithelial granulomas and interstitial
inflammation. Both the negative effects wthen developed into peribronchial inflammation
and necrosis. Shvedova (2008) who performed the same experiment, however, found out that
carbon nanotubes can lead to progressive fibrosis and increase in protein level other than
causing acute inflammation and progressive fibrosis. Other than the above mentioned illness,
the exposure of carbon nanotubes to the respiratory system may result in respiratory problems
such as asthma, bronchitis, emphysema and lung cancer. The entry of carbon nanotubes
through the gastrointestinal tract can also lead to Crohn’s disease and colon cancer while the
exposure of this nanoparticles to the circulatory system may cause heart disease and blood
clotting [ CITATION Sey13 \l 2052 ].

According to the 12th Sustainable Development Goal, which is responsible

consumption and production, sustainable consumption and production is about promoting
resource and energy efficiency, sustainable infrastructure, and providing access to basic
services, green and decent jobs and a better quality of life for all. During the synthesis of
carbon nanotubes, it is essential for the engineers to use less toxic substances. For instance,
substitute the toxic percursors into a less toxic percursors, and avoid the usage of highly toxic
precipitant and catalyst. It is also the engineers’ responsibility to ensure the correct
concentration of precursors ions are used in the synthesis process to ensure the nanoparticles
produced cause no harm to human.
 CHAPTER 5: FUTURE PROSPECT OF CARBON NANOTUBE

Nanomaterials provide unique multifunction properties due to their presences in the

nanoscale. Using nanoparticles such as TiO2, Fe2O3 SiO2 and especially carbon nanotubes
(CNTs) can greatly improve the microstructure and properties of cement matrix and make
them appear as promising fillers into many materials and engineering applications. The
addition of CNTs even at low level has become an appealing technique for enhancing the
mechanical, thermal, and electrical properties of polymer matrix composite materials or
cement. Epoxy resin has special mechanical, thermal and electrical properties, making it
suitable for different uses such as composites, laminates, adhesives and coatings that are
bonded with fibre. The application of epoxy-CNT composite onto glass fibers have also been
shown to reduce stress concentration and enhance electromagnetic shielding. The CNTs have
a high aspect ratio but they intermingle with each other and are difficult to be separated. The
addition of functional groups onto the surface of the CNT will facilitate effective adhesion to
the polymer and increase dispersion. Therefore, CNTs as a filler improve the epoxy resin
properties. CNTs have a lot of potential and application is wide, with more research and
development, it will definitely be very beneficial in the future. However, nanoparticles are
considered to be very costly, alternative ways are required to obtain the nanoparticles more
cost efficiently, in order for it to be more sustainable.
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