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WELCOME TO
NANOCOATINGS
WORLD

Coating

Component of Coating

Pigment Pigment are used decoratively as colorant or functional as anticorrosion or

magnetic pigment.

Binder The binder bonds the pigment particles to each other and to the substrate.

Additives - Substances added in small proportion to coating composition to modify or

improved properties

Fillers - Mostly used to extend the volume (low price), to confer or to improve technical
properties.

Solvent Liquid consists of several components and dissolved binders without chemical
reaction.

Nanocoating
Nanocoating are coating that produced by usage of

some components at nanoscale to obtain desired

properties.
Nanocoatings can be categorized as nanocrystalline,

multilayer coatings with individual layer thickness of

nanometers, and nanocomposites.
Nanostructured

coatings

offer

greatpotential

for

various applications due to their superiorcharacteristics

that are not typically found inconventional coatings.

FUNCTIONAL COATING
The term functional coatings describes systems which represent other than
the classical properties of a coating (decoration and protection). Functional
coating come up with additional functionality. This functionality depend
upon the actual application of a coated substrate.
Examples of functional coating

Expectations of functional coatings

Functional coatings perform by means of physical, chemical, mechanical and

thermal properties.

Chemically active functional coatings perform their activities either at:

Filmsubstrate interfaces (anticorrosive coatings),
In the bulk of the film (fire-retardant or intumescent coatings)
Airfilm interfaces (antibacterial, self-cleaning)

Air/ Film interfaces

properties
Bulk film properties
Film/ substrate
interface properties

1) Sacrificial
The use of a sacrificial anode such as zinc to protect steel is a long standing and wellknown industrial practice. The zinc layer on galvanized steel degrades when exposed
to an adverse environment, and this protects the underneath surface. Using a
similar approach, both inorganic and organic resin based, zinc-rich coatings have
been developed to protect a variety of metal substrates.

2) Barrier effect
Polymeric coatings are applied to metallic substrates to provide a barrier against
corrosive species. They are not purely impermeable. Moreover, defects or damages in
the coating layer provide pathways by which the corrosive species may reach the metal
surface, whereupon localized corrosion can occur.
Pigments having lamellar or plate-like shapes (e.g., micaceous iron oxide and
aluminum flakes) are introduced to polymeric coatings; this not only increases the
length of the diffusion paths for the corrosive species but also decreases the corrosion.
The orientation of the pigments in the coating must be parallel to the surface, and they
should be highly compatible with the matrix resin to provide a good barrier effect.
Layered clay platelets such as montmorillonite may also be introduced into organic
resin systems to increase the barrier effect towards oxygen and water molecules,
thereby enhancing the anticorrosive performance of the coating.

3) Inhibition
Primers containing metallic phosphate, silicate, titanate or molybdate compounds
are available as compounds used as corrosion inhibitors to formulate anticorrosive
primers for metallic substrate.
These pigments form a protective oxide layer on the metallic substrates, and often
also form anticorrosive complexes with the binder.

 High thermal-resistant coatings are required for a wide variety of metallic

substrates, including nonstick cookware, barbecues and boilers.
Fluorine or silicon-based products are used for the products. Fluorinated
coatings are not suitable for high-temperature applications as they
degrade above ~300 C and produce toxic by products. Siliconcontaining polymers offer better thermal resistance due to the high
energy required to cleave silicon bonds compared to carbon bonds in
analogous molecules.
Phosphorus containing compounds function by forming a protective layer
as a glassy surface barrier.
Expandable graphites also used as fire retardant; these contain chemical
compounds, including an acid, entrapped between the carbon layers.
Upon exposure to higher temperatures, exfoliation of the graphite takes
place and this provides an insulating layer to the substrate.

Figure: SEM micrograph of intumescent char obtained on an organic coating.

Consumer prefers to retain the aesthetic appearance of coated

materials and for this reason clear coats used on automobiles must
have good scratch and abrasion resistance.
Scratch resistance can be obtained by incorporating a greater number
of cross links in the coatings binder but highly cross linked (hard) films
have poor impact resistance due to less flexibility. A less-cross linked
(softer) film will show better performance with regard to other
properties such as antifingerprint and impact resistance but will have
less scratch and abrasion resistance. Thus, correct combination of
hardness and flexibility is required.

Self Healing/Cleaning
Coatings
The recent research in self healing coatings
is inspired by natural healing processes.
Self-cleaning coatings, as the name
suggests, have a special functional
property,
and today the term Lotus effect. That is,
the ability for a surface to repair itself after
naturally occurring or biological systems.

(a) Scanning electron micrograph of lotus leaf. (b) Schematic depicting

the relationship between surface roughness and self-cleaning. (c)
Mechanism of self-cleaning action.
In 1997, Barthelott and coworkers showed that the self-cleaning
property of lotus leaves was due to their specialized surface
morphology and hydrophobicity.
This specialized morphology prevents dirt from forming an intimate
contact with the surface, while the high hydrophobicity makes the leaf
water-repellent. Consequently, as the water droplets roll onto the leaf
surface, they carry along the contaminants.

Microcaps
ule
Crack
a) Cracks form in the
matrix wherever
damage occurs.

Healing
agent
(b) The crack ruptures
the microcapsules,
releasing the healing
agent into the crack
plane through capillary
action.
Polymerized
healing agent
(c) The healing agent
contacts the catalyst,
triggering polymerization
that bonds
the crack faces closed

Self-cleaning II
photocatalytic
nanotitanium dioxide (TiO2)
Probably the most wide-spread application
ascribed to nanotechnology in the
construction industry. There are already a
great number of buildings worldwide
which have been treated with it.
Titanium dioxide is hydrophilic due to its
high surface energy, hence water does
not form drops on a surface coated with it,
but a sealed water film instead.

Photocatalyst TiO2
absorbs UV radiation
from
sunlight/fluorescent
lamps

These photoproduced
radicals are
powerful
oxidizing species
and can cause
the deterioration
of organic
contaminants or
microbials
pieces on the
particle surface.

Produce pairs
of electrons
and holes.

The positive-hole of
TiO2 breaks apart the
water molecule to
form hydrogen gas
and hydroxyl radical.
The negative-electron
reacts with oxygen
molecule to form
super oxide anion.
(Both known as
photo-produced
radicals)

Electron of the
valence band of
titanium dioxide
becomes excited
when illuminated by
light.
The excess energy of
this excited electron
promoted the
electron to the
conduction band of
titanium dioxide
therefore creating the
negative-electron (e-)
and positive-hole (h+)
pair.

MECHANISM of Self-cleaning
photocatalytic nanotitanium
dioxide (TiO )

Titanium dioxide to reduce

pollution and clean the air

Microorganisms
represent potential
threats for our
Antibacter
modern hygienic
ial
lifestyle.
Cause
Coatings
to
1. Problems of aesthetics
(discoloration of the
coating),
2. Risks to health and hygiene,
3. Biofilm development or
microbial corrosion in the
case of metallic substrates.

Bacteri
a
Fung
i
Viruse
s

The classical biocides function is to either by inhibit the growth of

bacteria (biostatic) or by kill them (biocidal).
New legislations and the possibility of bacterial mutation have forced
coating manufacturers to seek new alternatives.
Today, more emphasis is placed on the development of bio-repulsive
(without killing) antibacterial coatings. A wide variety of organic or
inorganic biocides are available commercially and these demonstrate a
wide variety of biocidal and biostatic mechanisms.

Schematic of biofilm formation by

microorganisms.
Nitric oxide (NO)-releasing solgels as potential
antibacterial coatings for orthopedic devices.
Bacterial infection due to an implanted medical
device is a potentially serious complication,
typically leading to premature implant
removal.
These coatings are intended for application
onto biomedical devices to prevent devicerelated infections caused by bacterial biofilms.

Antifouling Coatings
Problem:
The microorganisms cause inconsistencies in the coating surface
and create friction with the water. This friction decreases the
speed of the vessel and adds weight to the hull. Both of these
factors increase fuel consumption and inflate the cost of
maintaining the vessel. The ideal antifouling coating would prevent
marine growth as well as maintain a long performance life while
keeping within strict environmental regulations.

There are two main types of underwater antifouling coatings. Chemical

release coatings use biocides, or chemical toxins that are released into the
seawater and prevent marine organisms from attaching to the surface. The
toxins create a barrier that prevents the marine growth. In the past these coatings
were typically copper oxide. Some of the chemicals that give these products their
toxic properties include; cuprous oxide, mercury, copper, arsenic and
tributyltin oxide (TBT). Any combination of these chemicals provides a harmful
biocide to the aquatic environment.
Another type of underwater hull coating is an ablative, self-polishing coating
system. Ablative systems prevent marine sea life from attaching sufficiently to the
coating surface. The initial coating surface steadily dissolves in the seawater.
As the top layer dissolves, a new smooth layer is left behind to repeat the
process. The rate of replenishment is controlled and constant allowing a uniform
transition through each layer of the coating.

Schematic of critical biofouling stages

Fouling of hulls is a major problem for world

shipping.

Auckland University have discovered that the fouling of

vessels by marine creatures is greatly increased by the
underwater sounds generated by the vessels themselves.

Application of antifouling paint to a ship hull

Nanopolymer
Coatings
Conducting Polymer
A conductive polymer is an organic polymer semiconductor. They
provide pathways for electronic conduction by doping. Common
classes of organic conductive polymers include: Poly(acetylene)s,
Poly(pyrrole)s, Poly (thiophene)s, Poly(aniline)s etc.
Biosensor- Biosensor is an analytical device which converts a biological
response into readable signal. Bio sensor comprises of three
components: bioreceptor, transducer and detector.
Polypyrrole nanocomposites with oxides, especially with Fe3O4 have
prospects for use
in corrosion protection of iron.

Glucose monitoring device (for

diabetes patients)- Monitors the
glucose level in the blood.

Pregnancy test- Detects the hCG

protein in urine.

Self-assembled
nanophase
(SNAP) Coating

BEFORE
Conventional chromate conversion
coatings (CCC) work well for iron
and aluminum alloys in terms of
their corrosion protection
performance. However, the strong
oxidation properties of chromates
make them a potential lung
carcinogen responsible for the
DNA damage.
For primer coating applied solgel
derived thin films. Solgel films
have good adhesion to both
metallic substrates and organic
top coats.
However, they result voids
throughout the solid gel after the
drying procedure (Evaporation
process). Besides, they cannot
provide any active corrosion
protection or stop the propagation
of corrosion once corrosion is

AFTER
SNAP - potential replacement for
chromate-based surface treatments
on aircraft aluminum alloys.
This Self-assembled Nanophase
Particle (SNAP) process can be used
to form thin, dense protective
organic surface treatment coatings
on Al aerospace alloys. The ability to
design coating components from the
molecular level upward offers
tremendous potential for creating
multifunctional coatings.
The SNAP coating mostly be used as
part of a complete aircraft coating
system designed to protect the
aircrafts aluminum alloy from
corrosion. The coating steps include,
in order of application, surface
preparation, surface treatment
(SNAP), primer and topcoat.

Conventional Coating
System

SNAP Coating System

Nanoparticle/Fillers For
Coating

What is
nanoparticle
??

A
microscopic
particle with at
least
one
dimension
less
than 100nm.

Method for
Coating
TiO2 nanoparticles dispersion in
an epoxy resin matrix
TiO2 nanoparticles dispersed
when sliding against a smooth
steel counterpart
The friction and wear behavior of
nanocomposits sensitive to the
dispersion states of the
nanoparticles
The wear resistance could be
increased if the micro structural
homogeneity was improved
1. TiO2 Nanoparticle Dispersed In An Epoxy Resin (Min

2.
Epoxy-clay
nanocomposite
coating
Nanoparticle Dispersed In An Epoxy
(M.R.Bagherzadeh et al, 2007)

TiO2
Resin

3 samples containing different amount of clay (1.3 and 5%)

were prepared
The desired amount of resin and nanoclay was mixed
together and performed in an oil bath (50-70 degree)

The mixture was subjected to sonication for 8-12h

Addition of some additives to epoxy clay mixture
The stoichiometric amount of the hardener was added to
mixture
The clay loading increases the barrier and anti-corrosive
properties increases
The best anti-corrosive performance of coatings was
obtained at 3 and 5 wt % clay concentrations

Nanoparticles/Fillers For Coatings

Prepared nanosilica containing coatings by UV
curing of an epoxy system. They found that, surface
properties were modified with an increase on
hardness in the presence of filler.
Finally the strong decrease on water uptake in the
presence of SiO2 was noticed. These nanocomposite
materials can be a good choice for gas barrier
coatings applications.

3. Nano-CaCO3 Powder Coatings Using Epoxy

Resin/NanoCaCO3 (H.J.Yu et al, 2006 )
Nano-CaCO3 modified powder coatings was prepared
using epoxy resin/NanoCaCO3 composite by in situ
and inclusion polymerization
Compared with unmodified powder coatings
The tensile properties and neutral salt spray corrosion
resistance of the modified coating was improved
The dispersion of nanoparticles in the films effects on
the properties of resultant powder coatings was
greatly
Method of in situ and inclusion polymerization is
effective way to disperse nano-caco3 in the powder
coatings
This method can be a reference to make other kinds
of nanoparticle modified powder coatings

Conclusion
Protective coatings perform important functions based on types
of coatings. The application of nanotechnology in the
corrosion protection of metal has recently gained momentum
as nanoscale materials have unique physical, chemical and
physicochemical properties, which may improve the corrosion
protection in comparison to bulk size materials. Significant
work on nanoscale coatings is underway globally in the area of
the area of nanocoating in the way of incorporating
nanoparticles in coating formulation that enhance specific
features.

Q & A

Answer Question 1: Conventional Coating Vs

Nanocoating
Conventional coating

Nanocoating

Micron scale structure

Nanostructured materials

High contact tension between

water drop of and coating layer

Contact tension reduced (water

repellence)

Moisture can penetrate housing

Moisture penetration is minimized

Surface roughness is 5 m due to

larger particle size

Surface roughness reduce to 1 nm

for better dirt repellence

Physical, chemical, mechanical and

thermal properties

Improved the properties of

conventional coating

Answer Question 2: Preparation of

SNAP (Self-Assembled Nanophase
Protection)

SNAP Procedures
1. SNAP solutions were prepared by drop-wise addition of
42.8 glycidoxypropyltrimethoxysilane (GPTMS)
and 8.9 ml tetramethoxysilane (TMOS) to 64.8 ml
solution of 0.05 M acetic acid in doubly distilled
deionized (DDI) water.
2. The application solutions were prepared by diluting the
aged SNAP solution with water and subsequent addition
of a crosslinking agent (DETA) and surfactant.
3. The final mixture was vigorously stirred and applied to
the cleaned aluminum alloy panels by dip-coating.

2.0 Coating technique

2.1 Processing or coating
for organic coating
Spray coating

Dip coating

Dipping

Wet layer
formation

Solvent
evaporatio
n

Plastic dip coating

Stages of the dip coating process: dipping of the substrate

into the coating solution, coating of substrate (wet layer )
by solvent evaporation

2.2 Processing for inorganic and

hard coating
Conductive nanocoating on
textiles
atomic layer deposition(VCD)