Recent Studies On Carbon Nano Tube Based Functional Coatings With Respect To

Properties and Applications

Avishek Mazumder, Narayani Rajagopalan, Chinmaya Nayak

Shalimar Paints, Industrial R&D, Nashik – Mumbai highway, Gonde, Nashik – 422403
avishek.mazumder@shalimarpaints.com
narayani.rajagopalan@shalimarpaints.com
chinmaya.nayak@shalimarpaints.com

Abstract

Multi-walled and single walled carbon nanotubes (CNTs) are synthesized by methods namely ‘Arc discharge’,
‘Laser Ablation’, ‘Chemical Vapor Deposition’. Due to its unique properties CNTs are considered as the
backbone of futuristic coatings. As on date, it has wide area of usage right from medical and biomedical
sciences to high performance conducting coatings to aerospace and specific defense equipment coatings. The
techno-commercial aspect is brightest amongst all the nano-particle or composite systems available. CNTs are
basically products of rolled carbon sheets. Based on the sheets, the basic characterization of CNT happens and
is classified in two groups, namely, single walled or multi walled. CNTs are functionalized s to enhance its
performances which are more commercially viable, for example these functionalized CNTs are used in acrylic
system for automotive paints and incorporates advance coating properties in automotive paints like anti-dust,
superhydrophobicity etc. CNT coatings finds its application in a wide area of functional coatings like
windshields for anti-glare, anti-dust, anti-fog properties. The properties, their final application, process of
authentication of the properties, functionalization of CNTs and the works related to further modification of CNT
itself and coatings which can be modified by CNTs are discussed in this paper.

1. Introduction

Presently carbon nano tubes (CNTs), an allotrope of carbon are recognized as the material of high advantages
because of its high form factor i.e. length/diameter ratio, mechanical properties and electrical properties.
Graphene sheets are wound up to CNTs. They can be either single walled (SWCNT) or multi walled (MWCNT)
[1].

Cylindrical carbon molecules have unusual properties, which are valuable for nanotechnology, electronics,
optics and other fields of materials science and technology. Owing to the material's exceptional strength and
stiffness, nanotubes have been constructed with length-to-diameter ratio of up to 132,000,000:1, significantly
larger than for any other material [1].

In addition, owing to their extraordinary thermal conductivity, mechanical, and electrical properties, carbon
nanotubes find applications as additives to various structural materials. For instance, nanotubes form a tiny
portion of the material(s) in some (primarily carbon fiber) baseball bats, golf clubs, car parts or Damascus steel
[1].

There is no consensus on some terms describing carbon nanotubes in scientific literature: both "-wall" and "-

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walled" are being used in combination with "single", "double", "triple" or "multi", and the letter C is often
omitted in the abbreviation; for example, multi-walled carbon nanotube (MWNT) [1].

1.1. History of Carbon Nanotube (CNT)

Carbon nanotubes were discovered by Lijimaand co-workers in the year 1991[2]. Since then it has been the
subject of investigation for many around the world. Every work is done in keeping in mind about their high
aspect ratio. Their large length of several microns with a very small diameter only of few nanometers endows
CNT with extraordinary properties and is regarded to be the backbone of futuristic coatings.

Figure 1: Aspect ratio of CNT [2].

1.2. Morphology of Carbon Nanotube (CNT)

CNT belong to the fullerene family of carbon allotropes. It is basically sp² hybridized carbon atoms with the C-
C bond distance of 1.4Å. The cylindrical molecules are hexagonally arranged. The cylindrical shape of CNT
comes from rolling sheets of graphene seamlessly [2]. Depending upon the rolling of graphene sheets CNT can
be classified in two types i.e. “Single Walled Carbon nano tube (SWCNT)” and “Multi Walled Carbon Nano
Tube (MWCNT). The inner diameter of MWCNT generally is in the range of 0.4 mm up to a few nanometers
depending upon the number of layers. The axial size of it ranges from 1 µm to a few centimeters. SWCNT
diameters range from0.4 to 2 to 3 nm. The length of SWCNT generally lies in the micrometer range. It comes in
a bundle structure. SWCNT form a crystal like structure by organizing themselves hexagonally [2].

Figure 2: Model of CNT [2].

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There are three techniques by which CNTs are synthesized; mainly: arc discharge, laser ablation and chemical
vapor deposition (CVD) [2]. These techniques are considered as high end technologies and costly, also at the
same time, only lab grade materials are obtained till date. Currently, researchers are working for more
economical and feasible ways to produce CNTs.

2. Methods of synthesis

2.1. Arc Discharge

It is the easiest way of producing CNT and it is the simplest process to undertake. It was primarily used to
produce C60 fullerenes. This technique generally does not give pure nanotubes. CNTs have to be separated
from soot and the catalytic metals present in the crude product. In this process generally two carbon rods are
placed in 1mm distance and a direct current of 50 to 100 A and 20 V approximately is driven through it which
creates a high temperature. This vaporizes one carbon rod and deposits on the other rod in the shape of nano
tubes [2].

Figure 3: Arc discharge method [2].

2.2. Laser Ablation

In 1995, Smalleye's group reported at Rice University about the synthesis of CNT by laser ablation method.The
basic technique of this method is the temperature difference between hot and cold stages of helium or argon
filled oven. In this process of temperature fluctuation large clusters of carbon molecules gets deposited. Then
these clusters are then further processed to get crystallized CNT particles [2].

Figure 4: Laser ablation method of CNT synthesis [2].

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2.3. Chemical vapor deposition

This method was originally developed in the 1960s and 1970s and has been successfully used in the production
of carbon fibres and carbon nano-fibres formore than 20 years. Using this method, CNTs are produced from the
carbon containing source (usually gaseous form) as it decomposes at elevated temperature and passes over a
transition metal catalyst (typically Fe, Co or Ni). A high yield of nanotubes is achieved by this method, but the
nanotubes are more structurally defective than those produced by arc or laser evaporation methods. There are
several advantages of the CVD method, which make it preferred to other available synthesis methods. Firstly,
the product tends to be purer (far fewer impurities in the form of nanoparticles of graphite or metal). Secondly,
the growth occurs at a lower temperature (550–1000°C) making the process both cheaper and more accessible
for lab applications. Finally, the metal catalyst can be held on a substrate, which can lead to the growth of
aligned nanotubes in a desired direction with respect to the substrate [2].

3. Properties of CNTs

CNT owing to their unique chemical structure possess unique properties too. Carbon nanotube technology can
be used for a wide range of new and existing applications:

 Micro and nano-electronics

 Structural composite materials
 Flat-panel displays
 Conductive plastics
 Atomic Force Microscope (AFM) tips
 Ultra-capacitors
 Radar-absorbing coating
 Technical textiles
 Gas storage
 Power applications (e.g. batteries with improved lifetime, photovoltaic applications)
 Sensors and Biosensors
 Extra strong fibers [3].

Overall, carbon nanotubes show a unique combination of stiffness, strength, and tenacity compared to other
fiber materials which usually lack one or more of these properties. Thermal and electrical conductivity are also
very high and are comparable to other conductive materials. The intrinsic mechanical and transport properties of
carbon nanotubes make them the ultimate carbon fibers.

4. CNT Based coatings

4.1. CNT based Conductive coatings

C. M. Trottier et al. (2005) have reported that carbon nano tubes can be used in the transparent conductive
coatings [4]. Their work showed that how to incorporate SWCNT in modern conductive coatings altering ITO
and conductive polymers. The incorporation of CNT in conductive coatings enhanced the coating properties

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such as conductivity, abrasion resistance, good conductivity, excellent transparency, neutral color tone and
flexibility. They reported mainly about the optoelectronic properties and characterization of structure.

Figure 5: CNT film (250Ω) SPM image (2-µm scan size) showing morphology of CNT film [4].
.

Figure 6: Optical Visible-light transmittance of ITO, PEDOT and CNT films [4].

Figure 7: Color measurement of CNT, ITO and PEDOT films [4].

As seen from the results above, CNT films exhibited significantly higher transparency across the entire visible
light spectrum. CNT films were observed to be more transparent than PEDOT films. The color measurements
confirmed that CNT films were much closer to neutral color than both ITO and PEDOT.

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 Figure 8: Optoelectronic performance of CNT transparent conductive coatings [4].

CNT coatings were observed to exhibit sheet resistance over a large resistivity range from one order of
magnitude up to as high as 10 orders of magnitude.The mechanical and chemical functionality of the CNT
coatings were tested on specimens made via spray coating a purified CNT dispersion onto heat-stabilized
PETfilm. Testing was carried out at 0.7% strain amplitude, 1.25 Hz, and 25°C, and the resistance was measured
continuously throughout the experiment. It was found that CNT coating showed <0.5% change in resistance
after 2500 cycles, where as ITO control samples showed >2% change after only 1000 cycles. The degradation
in ITO resistance during flex testing was attributed to cracking of the ITO film and as flex cycling continues,
these cracks continued to grow leading to catastrophic failure. At these strain levels, this failure mechanism was
not observed. The chemical and heat resistance of the developed CNT films was evaluated and it was found that
CNT film exhibited excellent resistance to strong acid, organic solvents, and high-temperature exposure
(250°C), however, the CNT film/glass interface was readily attacked by this aggressive alkaline solution,
resulting in delamination of the CNT film. From the overall studies and going through the performance tests it
was concluded that transparent CNT electrodes can be used as most suitable alternative as of now, and can
replace ITO for display coatings with added advantages and performances [4].

Joong Tark Han et al. (2008) reported their work on transparent, conductive, and superhydrophobic films from
stabilized CNT/ silane sol mixture solution [5]. Display technologies, solar cells, flexible electronic devices,
automobiles, and optical devices rely on the technology of transparent conducting films based on carbon
nanotubes CNTs. According to their study the technology met the needs of a wide range of applications
requiring multifunctional coatings ranging from optoelectronic devices to structural coatings if the wettability of
the conductive CNT films was controlled from superhydrophobicity (contact angle (CA)>150 8) to
superhydrophilicity (CA<5 8).

It was suggested that the silane compound will introduce various chemical moieties on the top surface
andprovide particular mechanical properties whereas the CNT network will control the nanostructure of the
films. Multiwalled CNTs (t-MWNTs) with an average diameter of 3–5 nm and length ranging from hundreds of
nanometers to micrometers to fabricate the transparent, conductive, and superhydrophobic films.

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 Figure 9: FESEM images of the H2O2-treated t-MWNT/silane hybrid films (50wt.% silane content) a) without
and b) with silica nanoparticles c) FESEM image of a pure (100 wt%) [5].

Figure 10: Water CA (triangles) and sheet resistance (Rs) (circles) versus transmittance of CNT/silane hybrid
films (70 wt% silane content) without (open) and with (solid) SNs. The upper image shows water droplets on
transparent and conductive films [5].

The prepared t-MWNT solution was then mixed with the silane sol solution, which resulted in the formation of
a stable t-MWNT/silane sol (30:70 wt. %) solution. TEOS provided mechanical strength and hydrophilic
moieties to the coating film and the fluorinated silane or other alkoxy silanes having functional groups
facilitated control over the wettability of the coating film. The water contact angle gradually increased when the
spraying amountof the t-MWNT/silane sol solution was increased, which was attributed to the enhanced
roughness and the pore generation resulting from the CNT networks. It was observed that a water droplet on
this film formed a sphere with a CA of 153° at a sheet resistance of approximately 4.1x104 Ώ sq-1 and a
transmittance of 73%. The wettability of the CNT/silane hybrid films can be controlled from

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superhydrophobicity to superhydrophilicity by the varying the type of silane compound used in commercial
functional coatings and the combination of these silane compounds in sol mixtures allows the possibility of
fabricating highly functional conductive coatings, such as anti-reflection, antifouling, etc. It was concluded
from their studies that one-component CNT/silane sol solution can be used to create transparent, conductive,
and superhydrophobic or superhydrophilic films. Development of self-cleaning coatings for optoelectronics,
transparent film heating, electrostatic discharging, and EMI shielding, a wide range of applications for CNT-
based films can thus be achieved by combining unique properties of CNTs with the chemical functionality of
the silane binder [5].

4.2. CNT based Black coating

Santa Barbara Infrared (SBIR) and Surrey NanoSystems (SNS) collaborated to make CNT based coatings
branded as Vantablack and Vantablack-S, possessing extremely high surface emissivity for improved
radiometric calibration and stray light control [6]. They optimized the performance of CNTs by aligning them
vertically (Vertically-Aligned Nanotube Array, VANTA), which are equally spaced and have high aspect ratios.
The light entering these spaces get absorbed by multiple reflection in the tubes. This has got a forest like
structure of CNT alignment.

Figure 11: SEM images of Vantablackcoating at magnifications of 2500 X and Vantablack-s at 2750 X [6].

These CNT coatings were reported to be used as super black coatings as stray light controllers to enhance IR
radiometric calibration accuracy. The high absorbance nature of these coatings made IR’s extended area
blackbody sources to emit surfaces which are ideal for high accuracy for radiometric calibration in both MWIR
and LWIR spectral regions.

Figure 12: Comparison chart between Vantablack-s and Treatment A (paint commonly used for extended-area
Blackbody emitter plates of IR spectral emissivity) [6].

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The spectral emissivity of Vantablack-S to a commonly-used, high-emissivity coating was evaluated and it was
found that SBIR coating showed excellent optical properties from the near-IR out to wavelengths beyond 15μm.
The unique low reflectance characteristic of these CNT based coating thus made it ideal for reducing stray light
in both visible and infrared optical systems [6].

4.3. CNT coating for Orthopedic and Dental application

Elzbieta Dlugon et al. (2015) have reported their work which was supported by the NCN (National Science
Centre-Poland, Grant: UMO-2011/01/B/ST5/06424) on modification of titanium surface with multi-walled
carbon nanotube. In the field of orthopedic and dental implants the use of titanium and its alloys find the highest
uses. And for this intense medical application purpose theses alloys need better corrosion resistance properties
than regular biomedical products. CNT’s have found its high usage because of its unique biological properties.
Titanium alloys and titanium surfaces were coated with CNT via electrophoretic deposition (EPD) process. The
CNTs used were short CNTs (NanoAmor, width 1-2µm, outer diameter 10-30 nm and inner diameter 5-10nm),
functionalized and acid purified and dispersed in distilled water. This dispersion was then deposited on etched
(5% hydrofluoric acid) titanium plates. The EPD deposition of CNT layer on titanium surface was found to
create a fibrous mesh-like structure, confirmed by AFM (Atomic Force Microscopy) micrograph.

Figure 13: AFM images of CNT on titanium surface [7].

Figure 14: Tafel plots for Ti and Ti-CNT samples [7].

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Ringer’s solution was used to determine the difference of corrosion potential current between coated and non-
coated titanium surfaces. A lower corrosion resistance, and higher corrosion current, was observed for CNT
coated Ti sample compared to neat Ti sample. The surface of titanium modified in the EPD process is assumed
to be divided into two main parts – nanocomposite layer of CNT built into titaniumoxide and surface-most layer
of CNTs. The nanocomposite part was held responsible for the shift in corrosion potential to positive values.
The porous fibrousand conductive CNT layer on the surface contributed to noticeable decrease in corrosion
resistance and increase in corrosion current density. The corrosion experiments concluded that the CNT-coated
titanium is more prone to corrosion than unmodified titanium, however, the low Rp and high iCORR; values were
not related with corrosion processes of titanium sample but with the presence of thin, conductive, CNT network.

Figure 15: Loading and un-loading curve for CNT covered titanium in dependence from indentation depth [7].

The mechanical analysis of the force–depth curve indicated that the layer hardness is depth-dependent. The
indenter first pierced low-density CNT layer thenreached composite of CNT built into titanium oxide formed in
the EPD process, resulting in a high toughness and low elastic modulus of the material.The surface-most part of
the coating exhibited mechanical and electrical parameters. The deep layers of the nanotubes created chemical
bonds with titanium oxideformed directly on titanium surface, resulting in strong bonding of the coating to the
titanium surface.

Figure 16: Viability of host cells after 3 and 7 days culture on different surface [7].

The biological analysis of cell viability in contact with samples after 3 and 7 days of incubation is seen in figure
17. After 3 days, the viability of cells on the titanium and CNT modified surface is lower in comparison to the
control. However, after 7 days culture cell viability on both samples is significantly enhanced compared to the

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third day of culture. The highest viability is obtained on the surface modified with CNT. The results indicated
that CNT modification of the biocompatible titanium surface significantly improved the biological properties of
titanium under study. The cell morphology on the surface of titanium and CNT-modified titanium after 7 days
showed the cells exhibited proper morphology. Both nucleus and cytoplasm were clearly visible in the images.
The study proved that the carbon layer promoted adhesion of bone cells. The acquired coating was found to
shield titanium from corrosion as well as gave the surface enhanced osteointegrative properties [7].

Figure 17: Host cell morphology stained with acridine orange on Ti surface (A) and CNT-covered Ti surface
(B) after 7 days of culture [7].

4.4. CNT Coating for Supercapacitors

Modern day batteries are being replaced by supercapacitors because they charge very quickly, andwork at
almost 100 percent efficiency. The main drawback regarding supercapacitors is their heavy weight. Researchers
at the Indian Institute of Science (IISc) have come up with idea of efficient, compact and lightweight
supercapacitors printed on plastic sheets.

Figure 18: Printed supercapacitors [8].

The traditional lithography used to fabricate supercapacitors, creates bulk structures with less surface area for
charges to move and is also expensive and time-consuming. The scientists of IISc used a simple spray method
to apply thin and altering layers of MnO2-coated carbon nano tubes (CNTs) and reduced graphene oxide (rGO).
They stacked these layers on top of stainless steel mask mounted on PET plastic sheet. This type of patterning
positioned the materials strategically for charges to move efficiently as the surface area got increased by this
method of application. The layered hybrid supercapacitor showed a muchlarger capacitancecompared to
structures that hadonly CNT, only rGO, or a random mix of the two materials. It also showed greater storage

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capacity than existing supercapacitorsreported to date. It was concluded that CNT-rGO based supercapacitors
were utilized as flexible energy storage applications [8].

4.5. CNT Coating for Automobile Application

Osiel Lucas Flores et al (2012) have reported their work on enhanced physical properties of automotive acrylic
paint modified with three different types of carbon nanotubes: single wall carbon nanotubes (SWCNTs), OH-
functionalized single-wall carbon nanotubes (OH-SWCNTs), and aniline-functionalized single-wall carbon
nanotubes (aniline-SWCNTs) [9]. The studies showed that the acrylic paints with addition of OH-SWCNTs and
aniline-SWCNTs showed better quality performances. The resistance against degradation by electron beam
increased significantly by ∼500%. The CNT’s were incorporated into the acrylic paint by direct aggregation of
nanotubes which were prepared by varying the percentage of SWCNTs.

Figure 19: Synthesis of functionalized carbon nanotubes [9].

The TEM and SEM results showed that the SWCNTs, functionalized with amino-isophthalic acid were
connected with another one can and formed larger structural net, imparting enforcement to the polymer matrix.
TEM image of p-anisidine modified SWCNTs interaction of two nanotubes resulting in formation of ring. The
increase of tension of carbon “lines” on the nanotube surface is attributed to the methoxy group (–O–CH3) in
the benzene ring.

Figure 20: (a) TEM image of the sample of (amino-isophthalic acid)-SWCNTs and p-anisidine-SWCNTs (b)
SEM image showing interconnections of two nanotubes [9].

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Figure 21: SEM image of the sample P1SWOH4 distribution of nanotubes in the matrix, (b) OH-SWCNTs after
degradation of the matrix [9].

It was found that the SWCNTs presented a low level of homogenization in the acrylic paint. The paint
composite after incorporation of OH-SWCNTs showed very high particle homogenization level due to the
presence of OH-groups and increased the capacity of covering material surface of the paint up to 30%. High
homogenization level was reached with incorporation of anisidine-SWCNTs, leading to increase of the capacity
of covering material surfaceby the paint up to 30%. Composite (OH-SWCNTs and anisidine-SWCNTs) paints
possessed a higher hardness and a rapid dissipation of temperature was observed during the drying process at
200°C. It showed better performance than original paint or the paint with incorporated non-functionalized
nanotubes. The thickness of the final layer of the formed paint played a role into this property of higher
hardness and a rapid dissipation of temperature. The fastness of thermal dissipation was calculated in a
temperature range 25 to 180°C per minute, approximately. The fastest dissipation was found in the paints,
whose samples corresponded to P1SWOH, for example, the major fastness of 51.66°C/min was observed for
the sample P1SWOH4, an OH-SWCNT acrylic paint. Thus it was recommended for industrial applications to
use OH-SWCNTs due to the quality of thickness of the layer and the capacity of thermal dissipation.

Figure 22: Relation between the fastness of thermal dissipation and thickness of the final layer [9].

The incorporation of SWCNTs increased the resistance of the resulting composite paint against degradation.
The effect of the SWCNTs on the resistance of paints against degradation up to ∼500% is as shown in
following figure.

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 Figure 23: Degradation of sample (1) Target (2) P1SW3 (SWCNT) (3) P1SWOH4 (OH-SWCNT)
(4) P1SWFC4 (anisidine-SWCNT) using the electron now of 30 kV [9].

The effect of the OH-SWCNTs and anisidine-SWCNTs, being incorporated in a automotive paints,
corresponded to the ∼500% higher resistance against degradation by electron flow of 30 kV in comparison with
the paint without incorporation of SWCNTs. Results showed that incorporation of OH-SWCNTs in the
automotive paint was chosen as the best additive to improvethe physical properties of the composite paint [9]. It
was proved that physical properties of the composite paint was considerably improved by incorporation of OH-
SWCNTs, leading to high capacity of the applied paint (ability to cover surfaces), fastness of thermal
dissipation, high homogeneity in the paint matrix and, possibly, high probability of inhibition of solar
degradation [9].

4.6. CNT Coating for Tribological Application

Composite coatings with excellent performances are of prime importance for the development of the modern
automobile industry and in advanced space applications. The traditional electroless composite coatings, such as
Ni–P–SiC, Ni–P–BN and Ni–P–graphite, have been used as anti-wear films in many fields because of their high
wear resistance. W. X. Chena et al. (2002) studied about the tribological application of carbon nanotubes in a
metal-based composite coating and composites [10]. Electroless plating and powder metallurgy techniques were
used to prepare Ni–P–carbon nanotube (CNT) composite coating and carbon nanotube/copper matrix
composites. The results showed that higher wear resistance and lower friction coefficient property was
exhibited by the Ni–P–CNT electroless composite coatings rather than Ni–P–SiC and Ni–P–graphite composite
coatings. The experiments were carried with multi-walled carbon nanotubes, synthesized bychemical catalytic
vapor deposition (CCVD). Ni–P–CNT composite coating was deposited on amedium carbon steel substrate by
electroless plating. A specific electroless bath composition and condition was maintained. The coating
thicknesses were maintained as 8–10 and 35–40 mm in Ni–P and Ni–P–CNT composite coatings and in case of
the Ni–P–SiC and Ni–P–graphite coatings respectively. It was observed and confirmed from XRD studies that
the microstructure of the coated panels changed from amorphous to typical crystalline state and the Ni P3 phase
forms in the Ni-matrix, after treating it in 673 K for 2h. Due to this typical phenomenon, these electroless
coatings exhibited improved wear resistance consequently increasing the microhardness.

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 Figure 24: XRD patterns of coated samples after annealing @ 673K for 2 hours [10].

The Ni–P–CNT composite coating exhibited higher wear resistance and lower friction coefficient in comparison
with Ni–P, Ni–P–SiC and Ni–P–graphite electroless coatings, and both beforeand after annealing at 673 K. The
mass loss of the Ni–P–CNT coating is about 1/5 of that of Ni–P, and also less than that of Ni–P–SiC and Ni–P–
graphite coatings. The friction coefficient of the Ni–P–CNT composite coating hardly changed before and after
treatment at 673K, and was observed to be 0.063 and 0.061, respectively. For the other electroless coatings,
friction coefficient decreased to some extent after heat treatment at 673 K. Thus it was concluded that CNTs
significantly improved the tribological performance of electroless composite coatings. Their improved
mechanical characteristics were attributed to the unique topological structure of the central hollow nanotubes.
The wear and friction studies showed that the friction coefficient of Ni–P–SiC coating, which is known to be
highly wear resistant, was higher than that of the Ni–P–CNT composite coating, and its mass loss was also
comparatively larger. It was reported that the CNTs in the composite coating during the wear and friction test
slowly released onto the metal surface and served as spacers, preventing rough contact between the two mating
metal surfaces, lowering the wear and friction rate drastically. Small CNTs slide or roll between the two
matingmetal surfaces, resulting in a decrease in the friction coefficient. The friction coefficients slightly
decreased with increasing volume fraction of CNTs in the Cu-matrix composite, suggesting that an increase in
surface fraction of CNTs reduced direct contact between the metallic matrix and the diamond pin and modified
the friction due to self-lubrication of CNTs, thus resulting in the decreased friction coefficient of the
composites. The wear rate of the Cu-matrix composite was found to be dependent on both the microstructure
and the applied load.

Figure 25: Friction coefficients of Cu-matrix CNT composites at different applied loads [10].

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Coatings with excellent tribological performance is the area where CNTs are leaving any other material far
behind. Their studies also showed that both Ni–P–CNT composite coating and CNT/Cu-matrix composites
showed higher wear resistance gradients than its traditional counterparts. The tribological properties of the
composites and coatingwith CNTs were significantly improved [10].

4.7. CNT based Camouflage Coating

Dr. Xiaowu (Shirley) Tang has reported his work on carbonnanotube coating for visible and IR camouflage
background [11]. His work showed a possibility of a coating along with a layered structure that renders
invisibility in visible light and IR detection. Night vision devices are generally categorized in three categories
like the device which simply amplifies visible light reflected from objects at low lighting condition which is
regarded as type I. The device which is equipped with an IR source and detects reflected IR from objects in dark
is marked as type II. The device which detects thermal IR emitted from objects such as a human body
categorized as type III. A coating was found based on CNT and a layered structure which was capable of
counteracting all three types of night vision devices. The carbon nanotube (CNT) coating was known for its
anti-reflective in both visible and an IR range property and to add on, it also had a wide absorption spectrum of
0.2 to 200 μm range. Traditional type III devices generally contain metal or metal compounds which are highly
reflective and can be easily detected by type I and type II. The specialized developed coating consisted of one or
more layers of CNT coatings and insulators. This layered structure was designed to counteract the thermal IR
detection which is type III. The insulator thermally isolated the CNT coating from hot objects. A hot object such
as human body emits IR which gets absorbed by the CNT coating effectively. CNTs fast thermal equilibrium
with its surrounding environment property comes due to their high thermal conductivity and low mass of CNT
coating.

Figure 26: Difference in IR reflectance of a CNT coated and uncoated surface [11].

It was found that only the CNT coating is sufficient in case of anti-Type I & II detection no insulator layer is
required. His study concluded that this technology introduces a novel coating system which can be used or
applied over fabrics to enable night vision invisibility. It can also find application in IR camouflage, stealth
coating and military clothing [11].

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4.8. CNT Coating for Defense Application

Prof. L. Jay Guo reported in 2011 about the fact that nano paint can make airplanes invisible to radar [12]. The
work reported that the carbon nanotube (CNT) coating can be used to cloak an object in utter darkness and
make existence of any object indistinguishable from the night sky. Besides their brilliant and other technical
properties CNTs are also the blackest known material. It can absorb a broad spectrum of light from radio waves
through visible light through the ultraviolet almost perfectly because of its long straws of pure carbon, each just
a few nanometers in diameter which is the main reason behind its absorption.

Figure 27: Carbon camo: A coating of carbon nanotubes, visible in the scanning-electron micrograph at left,
makes the tank pattern invisible under a light microscope at right [12].

A sparse forest of vertical carbon nanotubes on the surface of various three-dimensional objects was aligned
including a silicon wafer patterned with the shape of a tiny tank. The tank disappeared against a black
background because the nanotubes made the objects appear completely flat and black. Light is neither scattered
nor reflected off a nanotube-coated object. Light can’t scatter out of the nanotubes without being absorbed
because of the fact that nanotubes are perfectly absorbing and when they grow they are grown with some space
between them that is why their index of refraction is nearly identical to that of the surrounding air. Nanotubes
are relatively easy to make and work across a broad spectrum. CNTs shield objects by manipulating incident
light so that it simply flows around them. Materials that can achieve this property are to be made very
painstakingly and typically only work with a very narrow spectrum of light like microwaves or green or red
light but CNTs have a wide range. It was concluded from his work that it is possible to grow the nanotubes on
the surface of tiny particles which can then be suspended in paint which will make objects invisible to night sky.
This will find a broad application in defenses and national security purposes [12].

5. Summary

CNTs have a unique set of electrical, mechanical and thermal properties. Due to the greatest potentials of CNTs,
it is clear that novel coating application technologies will emerge in the near future. It is concluded from the
studies of the papers that the use of CNT improves the overall functional properties of paints. It incorporates
such properties in paint film so that the paint gets an edge over its rivals in the commercial aspect as well as
technically.

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REFERENCES

1. United States Patent, Patent No.: US 7.622,059 B2BOrdere et al. (45) Date of Patent: Nov. 24, 20092).

2. Rohini Chavan, Ujwala Desai, Priti Mhatre, Ruchira Chinchole, “A Review: Carbon Nanotubes”, 25-02-
2012.

3. Keld Alstrup Jensen, Jesper Bøgelund, Petra Jackson, Nicklas Raun Jacobsen, Renie Birkedal, Per Axel
Clausen, Anne Thoustrup Saber, Håkan Wallin, Ulla Birgitte Vogel, “Carbon nanotubes”,
Environmental project No. 1805, 2015, ISBN no. 978-87-93352-98-8.

4. C. M. Trottier, P. Glatkowski, P. Wallis, J. Luo, “Properties and characterization of carbon-nanotube-

based transparent conductive coating”, Journal of the SID, 13/9, 2005, 759-763.

5. Joong Tark Han, Sun Young Kim, Jong Seok Woo, and Geon-Woong Lee, “Transparent, Conductive,
and Superhydrophobic Films from Stabilized Carbon Nanotube/Silane Sol Mixture Solution”, Journal of
Advanced Materials, 2008, 20, 3724–3727, DOI: 10.1002/adma.200800239.

6. Gabe Amparan “Carbon Nanotube-Based Coatings Provide Extremely-High Surface Emissivity for
Improved Radiometric Calibration and Stray Light Control”, Santa Barbara Infrared (SBIR) and Surrey
NanoSystems (SNS), http://www.sbir.com/datasheets/VANTABLACK-S_White%20_Paper.pdf

7. Elzbieta Dlugon, Wojciech Simka, Aneta Fraczek-Szczypta, Wiktor Niemiec, Jaroslaw Markowski,
Marzena Szymanska and Marta Blazewicz, “Carbon Nanotube-based coatings on Titanium”, Bulletin of
Materials Science, Volume 38, No. 5, September 2015, 1339–1344.

8. Ranjini Raghunath, “Compact and flexible supercapacitor developed using simple spray coating
method”, July 9, 2018, https://phys.org/news/2018-07-compact-flexible-supercapacitor-simple-
coating.html.

9. Osiel Lucas Flores, Oxana V. Kharissova, Ubaldo Ortiz Méndez, Héctor Leija Gutiérrez, Edgar de
Casas Ortiz, and Boris I. Kharisov, “Application of Functionalized SWCNTs for Increase of
Degradation Resistance of Acrylic Paint for Cars”, Journal of Chemistry, Volume 2013, Article ID
573570, http://dx.doi.org/10.1155/2013/573570.

10. W. X. Chen, J. P. Tu, L.Y. Wang, H.Y. Gan, Z. D. Xu, X. B. Zhang, “Tribological application of carbon
nanotubes in a metal-based composite coating and composites”, Journal of Carbon, 41, 2003, 215–222.

11. Dr. Xiaowu (Shirley) Tang, “Carbon Nanotube Coating for Visible and IR Camouflage”,
https://uwaterloo.ca/research/sites/ca.research/files/uploads/files/uw_cnt_stealth_coating_ncs_7284_201
4.pdf, U.S. and PCT patent applications filed, Reference 8810-7284.
.
12. L. Jay Guo, www.technologyreview.com/s/426276/nano-paint-could-make-airplanes-invisible-to-radar.

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