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CHAPTER 1
INTRODUCTION
Paint is a viscous suspension containing binder, solvent, pigments, extenders and other
additives. The binder can be natural drying oil or resin. The solvent is added to the binder to
adjust its consistency so as to be convenient for application on a substrate in required thickness
depending upon the method of application used.
Most paints include at least four groups of components: binders, volatile substances,
pigments, and additives.
1.1 Pigments
Pigments are generally added in considerable proportion (360% by weight) to paint
formulations and are used to provide color, opacity, and sheen. They also affect the viscosity,
flow, toughness, durability, and other physical or chemical properties of the coating, such as
corrosion protection.
Pigments can be classified as either natural or synthetic types. Natural pigments include
various clays, calcium carbonate, mica, silica, talc etc. Synthetics would include engineered
molecules, calcined clays, precipitated calcium carbonate, and synthetic pyrogenic silica, etc.
The most important and established uses for organic pigments include the coloration of
coating compositions for interior, exterior, trade and automotive applications, including oil and
water emulsion paints and lacquers. Azo pigments are formed by successive diazotization of a
primary amine and coupling.
Inorganic pigments are an integral part of numerous decorative, protective and functional
coating systems, as found in automobile finishes, marine paints, industrial coatings, maintenance
paints, and exterior and interior oil, alkyd and latex house paints.
1.2 FillersFillers are a special type of materials that serves to thicken the film, support its structure
and simply increase the volume of the paint. Fillers are usually made of cheap and inert materials
like talc, lime, clay, etc. Floor paints that will be subjected to abrasion may even contain fine
quartz sand as filler. Not all paints include fillers. On the other hand some paints contain very
large proportions of filler.
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1.3 Binder/vehicle/resin
The binder, commonly referred to as the vehicle, is the actual film forming component of
paint. It is the only component that must be present; other components listed below are included
optionally, depending on the desired properties of the cured film. The binder imparts adhesion,
binds the pigments together, and strongly influences such properties as gloss potential, exterior
durability, flexibility, and toughness. Binders include synthetic or natural resins. They create
continuous coatings that stick to surfaces and remain in place indefinitely. In almost all cases,
these coatings are polymers. These molecules are interlock with one another like noodles.
Depending on the paint, these long molecules may already exist in the paint before application or
they may form as the paint "dries."
1.4 Solvent
The main purposes of the solvent are to adjust the curing properties and viscosityof the
paint. It is volatile and does not become part of the paint film. It also controls flow and
application properties, and affects the stability of the paint while in liquid state. Its main function
is as the carrier for the non volatile components. In order to spread heavier oils (i.e. linseed) as in
oil-based interior house paint, thinner oil is required. These volatile substances impart their
properties temporarily-once the solvent has evaporated or disintegrated, the remaining paint is
fixed to the surface.
Solvent-borne, also called oil-based, paints can have various combinations of solvents as
the diluent, including aliphatic, aromatics, alcohols, ketones and white spirit. These include
organic solvents such aspetroleum distillate,esters,glycol ethers.
1.5 Additives
Besides the four main categories of ingredients, paint can have a wide variety of
miscellaneous additives, which are usually added in very small amounts and yet give a very
significant effect on the product. Some of them include modification ofsurface tension, improve
flow properties, improve the finished appearance, increase wet edge and improve pigment
stability, etc.
1.6 Paint Manufacturing process General procedure
a. Mixing the pigment with sufficient vehicle to make a paste which has the correct
consistency for grinding
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b. Grinding the paste on the mill until the aggregates is broken down as indicated by the
fineness of grinding test.
c. Letting down the ground paste with the remainder of the materials in formula.
d. Tinting the batch to the required color.
e. Testing physical properties and performance requirements.
1.7 Objectives of the study
The aim of the work is to prepare the nano formulated paint and compare the properties
of this nano formulated paint with conventional paint.
Synthesis of iron oxide, titanium dioxide, prussian blue and graphene oxide nano
particles by gel-combustion method, size reduction method, wet chemical method and
hummers method.
Characterization of the nano particles by FTIR, XRD, SEM, AFM etc.
The paint will be prepared by desired composition which can be assigned by trial
method. Prepared paint film was applied on the prepared mild steel by brush coating
method. On spreading sheet by draw down method at 150m.
The corrosion inhibition of nano formulated paint coated mild steel and commercial paint
coated mild steel in 1N HCl solution was studied at 24 hours at room temperature by
weight loss method. The corrosion rate and inhibition efficiency are calculated using
formula. The dry film property was studied for nano formulated and commercial paint by Hiding
power, spreading area, Glossing test, finishing test, solid content and drying time.
CHAPTER 2
LITERATURE SURVEY
Limited number of literatures are available since it is a commercially important product.
T. Mizutani et al (2006) studied the Application of Silica-containing Nano-composite
Emulsion to Wall Paint: A new environmentally safe paint of high performance. They
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prepared Nano Composite Emulsion (NCE) paint. It was prepared using silica
nanoparticle and nanosized polyacrylate. The various paint property has been studied.
Solvent resistance and anti- pollution property also studied.
Problem: Compare to the solvent type paints, emulsion type paint is not more
efficient. Drying of the film is very quick. Additives are needed to form a product.
Ashavani Kumar et al prepared (2008) Silver-nanoparticle-embedded antimicrobial
paints based on vegetable oil. They used metal nano particle like silver nano particle has
been dispersed in to vegetable oil. The vegetable oil was used as binder. Silver nano
particle possessed antibacterial property and it has been proved by testing method.
Characterization of the paint was studied by using TEM, SEM, AFM.
Problem: Some vegetable oils are having inflammable nature.
Susana Cabello reported (2010) Nano Scratch /Mar Testing of Paint on Metal Substrate
the scratching tests on the metal surface by using the Nanovea Mechanical Tester. The
process of scratching in a controlled manner to observe sample behaviour effects was
studied. In this application, nano scratch testing was performed on 7 year old 30-50m
thick paint sample on a metal substrate. A 2 m diamond tipped stylus has been used at a
progressive load ranging from 0.015 mN to 20.00 mN to scratch the coating. They
performed a pre and post scan of the paint with 0.2 mN load in order to determine the
value for the true depth of the scratch. The true depth analysis for plastic and elasticdeformation of the sample during testing had been done.
Problem: In this method the scratching test is studied by using Diamond Tip.
P.Patel et.al. (2011) analyzed the Surface Coating Studies of Polyurethane Derived from
Isocyanate Terminated Caster Oil Mixture. In this the Castor oil (C) had reacted with
commercial epoxy resin (E)). Isocyanides terminated castor oil polyurethane had
prepared by the reaction of caster oil and hexamethylene diisocyanate. Alkyd resin had
blended with various proportions of CEs and ICBPU. A unique solvent system, which
showed one phase clear solution and a clear coat of binder system had used. All the
blends had applied on mild steel panels and tested like drying time, adhesion, flexibility,
hardness, impact resistance and chemical resistance properties.
Problem: The chemicals are highly toxic and irritating and it is also hazardous to
human health.
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Kathrin studied the Innovative use of Ultrasound in the Manufacture of Paints and
Coatings (2011). He reported the addition of nano-sized particles in the prepared paint
coatings and thus found increased scratch resistance and UV stability. Novel colors and
coating has been produced by using titanium dioxide, zinc oxide, alumina, ceria, silica.
Conventional devices such as high shear or shear mixer, high-pressure homogenizers or
colloid and disk mills had not deliver sufficient power to separate nanomaterial into its
individual particles. Particularly for substances in the range of a few nanometers to a few
micron meters the high power ultra sound method was used.
Problem: The cost of production is more. At high speed the agglomarization of
particles takes place, heat is also generated.
Energy simulation of heat shield coating on the way to green building for a sustainable
development (2010) by Suresh Chandra Pattanaik reported as the project was purely
based on the green environment technology .The green coating was prepared by using bio
based polymers like methyl soyate, mineral spirit, ethyl locate & ethylene glycol and it
was mixed with suitable ingredients. The bio based coating was applied on the exterior
walls, roofs etc. The excellent heat shield property has been observed.
Problem: This is Conventional Method. The raw materials are in micron size and
above.
Silver nanoparticles: Protective paints (2008) by Gemma Moxham, studied theantibacterial property in the glass plate by coating with silver nanoparticle and also
studied the compression between the ordinary paint and silver nano particle implemented
paint.
Problem: It is studied in glass plate only.
Self-Sealing Crystalline Coating and Self-Cleaning Nano coating for the Concrete
Substrate for a Sustainable Development by Suresh Chandra Pattanaik they reported that
the self-cleaning property on the concrete structure by applying the self-sealing
crystalline coating; it includes the crack resistance surface at the concrete structure.
Problem: This method is studied in the concrete structure as coating.
Nanomaterials in the Construction Industry: A Review of Their Applications and
Environmental Health and Safety Considerations reported by LEE et al. they reported
the use of nano materials property in concrete structure .The nano materials like carbon
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based nano particle and metal based nanoparticle. The carbon based nanoparticle like
carbon nanotube enhanced mechanical durability of the concrete structure and prevent the
crack formation. Metal based nano particle like TiO2 increased degree of hydration in the
concrete structure and also improved the self-cleaning property.
Problem: These properties are studied in concrete structure as coating.
In this project work, it is proposed to prepare the oil paint by using the nano particle as a
pigment. The specialized pigment is also used to enhance the paint property which is applied on
the steel plate and the property of paint film will be studied. The metal based nanoparticles are
used to prepare the paint, it having less toxicity; the preparation of the metal based nanoparticle
is not a complicated process.
CHAPTER 3
METHODOLOGY
Preparing nano formulated paint i.e. Hybrid paint using inorganic pigments like Ironoxide (red), Titanium dioxide (white), Prussian Blue (blue) and Graphene oxide (Black),.
Inorganic nanoparticles are used as pigments.
The characterizations of the nanoparticles are carried out using AFM/SEM/XRD/FTIR.
The pigments dispersed in the alkyd resin binder.
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The mixing and milling process is carried out in the planetary ball mill.
Prepared paint is applied on the suitable substrate by using brush coating method.
Properties of paint film are studied.
PREPARATION OF NANOFORMULATED PAINT
3.1 Synthesis of nano particles
3.1.1 Iron oxide
Iron nitrate 4.0g and citric acid 4.2g was dissolved in 50ml of distilled water and stirred
vigorously, during stirring ammonia solution was added drop wise and pH of the solution was
raised to about 10. The obtained sol was heated at 80oC in a hot plate with continuous stirring.
After certain period of time, self-combustion took place. The ash was formed, it was collected
and calcined in furnace at 700-800oC for a period of 2hours.
3.1.2 Titanium Dioxide
The titanium dioxide pigment was prepared by size reduction method using planetary ball
mill. The ball and the vessel were cleaned using a toluene solvent then it allowed to dry in the
atmosphere. Ball to Powder ratio was maintained as 10:1 for the size reduction. Based on ball to
powder ratio 37g of TiO2 was taken and loaded in the container. The TiO2powder in nano range
has been obtained after milling the container in 9 hours.
Figure: 3.1.2 Ball Mill
3.1.3 Prussian blue
0.5 m mol of citric acid was (98 mg) added to a 20 mL of 1.0 mM aqueous FeCl 3 solutionunder stirring at room temperature. In that solution 20 mL of 1.0 m M aqueous K4[Fe(CN)6]
solution was added under vigorous stirring. It contained the same amount of citric acid. A clear
bright blue dispersion was formed immediately. After stirring for 10 minutes, the solution was
allowed to cool down to room temperature with the stirring continued for 5 more minutes. In
order to separate the nanoparticles an equal volume of acetone was added to the dispersion.
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Centrifugation was done at 10,000 rpm for about 15 minutes, resulted in the formation of a pellet
of nanoparticles. The later was re-dispersed in 20 mL distilled water by sonication and it was
separated again by the addition of equal volume of acetone and centrifugation. The purification
process was repeated for two more times.
3.1.4 Graphene Oxide
The graphene oxide (GO) was synthesized by modified Hummers method using graphite
powder as the starting material [1]. Graphite powder (2 g) was stirred in 98% H2SO4 (35 mL) for
2 h. KMnO4 (6 g) was gradually added to the above solution while keeping the temperature less
than 20 C. The mixture was then stirred at 35-40 C for 30 min. The resulting solution was
diluted by adding 90 mL of water under vigorous stirring and a dark brown color suspension was
obtained. The reaction was terminated by the addition of 150 mL of distilled water and 30%
H2O2 solution (10 mL). After continuously stirred for 2 hrs, the mixture was washed by repeated
centrifugation and filtration using 5% HCl aqueous solution in order to remove the residual metal
ions. Further, the centrifugation process was repeated with distilled water until the pH of the
solution becomes neutral. Finally, a brown colored precipitate of graphitic oxide was obtained by
filtration and was allowed to dry under vacuum. Then the dried graphite oxide is redispersed in
150 mL of doubly distilled water and exfoliated into graphene oxide by ultrasound irradiation for
1 hr. After centrifugation, the graphene oxide nanosheets were dried at 60 C and stored.
3.1.5 Silver
0.85g of Silver nitrate was dissolved in 25ml of distilled water. The coriander plant leafs
extract was slowly added to silver nitrate solution with constant stirring. Stirring process was
carried out for 30minutes. During the course of that time the color of the solution was turned
black due to reduction of Ag+ ions into silver nanoparticle. After stirring, the reaction mixture
was centrifuged in order to separate the silver nanoparticle. The residue obtained after
centrifugation was washed thoroughly with distilled water, filtered and vacuum dried.
3.1.6 Substrate preparation
1% sulphuric acid was prepared by dissolving 1ml of conc. sulphuric acid in 100ml
distilled water. This solution was heated in the water bath at 50oC for 10 min. The steel plate was
dipped in this solution for 1min to clean the surface. Then the steel plate was polished by using
emery paper and cleaned with thinner. Over this cleaned substrate the paint was coated.
3.2 Preparation of paint using nano particles as pigments
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Based on the standard weight ratio to solvent volume, the nano pigments are dispersed.
Uniform suspension can be achieved by taking the desired materials in proper composition. The
mixture is then being grinded in ball mill.
Table: 1 Composition of paint
Ingredients Weight %
Total solids(pigments + additives) 50-70
Vehicle or medium 30-40
Solvents 20-40
The pigments synthesized in the above process is mixed with paint forming constituents
like binder(linseed alkyd resin) and other additives.
Vehicle or binder - linseed alkyd resin
Pigments - Red - Fe2O3
Blue - Prussian blue, Prussian blue with Ag
White - TiO2
Black - Graphene oxide
Thinner - toluene, MTO
Drier - cobalt naphthenate
Stabilizers - zinc oxideAdditives - soya lecithin, aluminum stearate, zirconia, thickener
After characterizing the common property of prepared paint, the anticorrosion
study was done using weight-loss method.
Table: 2 Composition between conventional and nano formulated paint
Conventional paint Nano formulated paint
Pigments +Additives +extender 30% * Pigments+ additives 22.4%
Binder 53% Binder 60.6%Solvent 17% Solvent 17%Milling Hours 12hours Milling Hours 5hours
Based on the above (Table 2) composition nano formulated paint was prepared by trial
method. This process was repeated until the correct compositions of paint have been achieved.
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Table: 3 Various constituents present in the paint
Materials Weight in gram Percentage %
Pigment 10 20
Binder(Linseed Oil) 30.3 60.6
Stabilizer(ZnO) 0.25 0.5
Thickener & antisettling Agent 0.25 0.5
Wetting agent(Soya Lecithin) 0.25 0.5
Inner Coat Drier(Zirconia) 0.25 0.5
UpperCoat drier(Co.Naphthanate) 0.20 0.4
Thinner 8.5 17
Total 50 100
3.3 Properties of Paint film
3.3.1 Corrosion inhibition
The studies of mild steel corrosion in acidic media receive more and more attention both
of academics and industrials because of the wide applications. Corrosion is the destructive attack
to metal by chemical or electrochemical reaction with its environment. Mild steel was easilycorroded in acidic medium. To reduce this problem the corrosion inhibitor coating was done on
it. A corrosion inhibitor is the material which inhibits the corrosion reaction by providing a
protective barrier film which in turn stops the corrosive reaction. Paint is a material which
prevents the direct contact of corroding media like air and H2O over the metal surface. It forms a
uniform thin layer after drying and protects the base metal from the corrosion. The corrosion
inhibitors impregnated nanoformulated paint is applied over the steel plates which increases the
corrosion efficiency. Many researches provided the inhibition of corrosion by adsorption of
inhibitors on the metal surface. Then compounds can adsorb on metal surface and block the
active surface sites to reduce corrosion. It has been speculated that metal oxides inhibitors are
more effective with iron [2-3]. Due to the aggressiveness of hydrochloric acid and sulphuric acid
in the solution against structural materials such as mild steel, the use of corrosion inhibitor
impregnated nano formulated is usually required to minimize the corrosion attack. Therefore in
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this investigation, the corrosion inhibition of mild steel in 0.1N HCl solution was studied in the
presence of metal oxide nanoparticle impregnated nanoformulated paint coated substrate at 24
hours in ambient condition by weight loss method. Because metal oxide having a tendency to act
as corrosion inhibitor with alkyd resin medium
3.3.1. a Preparation of specimen
The mild steel strips were cut into pieces of l x b (5 2 cm) and are pickled in pickling
solution (1% H2SO4) for 3 minutes and washed with distilled water. After drying, the steel plates
were polished with various grades of emery papers and degreased using acetone. Three surface
cleaned substrate was weighed and one strip was taken as reference, another strip was coated
with nano formulated paint and third one was coated with commercially available paint of the
same colour. Each strip weight was noted after drying and immersed in 0.1N HCl solution for 24
hours at room temperature in three different beakers containing 0.1 N HCl solution After 24
hours strips were taken out from the beakers and dried in room temperature then the weight of
the each strips were noted. The corrosion rate was calculated by weight loss method using the
following equation [4].
(1)
Where
Wt. Loss = weight loss,
C.R unit = mg/dm2.day
Similarly, inhibition efficiency was calculated using the equation [4],
(2)
Where
IE % = Inhibition Efficiency
W0 and Wi are the values of the weight loss in (g) of mild steel (plain) and paint coated
respectively.
3.3.2 Solid content of the paint
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(W0- W
i)
IE% = X 100W
0
Wt.Loss X 372Corrosion rate (C.R) =
Area X Time
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Thoroughly cleaned watch glass was weighed in the balance noted as W1in gram. 1+ 0.1
gram amount of paint was added over it and its weight was noted as W 2. Then it has been heated
in hot air oven for 1hour at 110oC. Then it was allowed to cool for 10 minutes. After cooling the
weight was noted as W3 g. Solid content of the paint was calculated by using the following
formula.
(3)
Where W1 = weight of the empty watch glass
W2= weight of the watch glass with paint
W3 = weight of the watch glass with paint after 1 hour heating.
3.3.3 Gloss Test
Figure: 3.3.3 Gloss measurement and standards
MPI gloss and sheen standards
Gloss Level Description Gloss at 60 Sheen at 60
Gloss Level 1 a traditional matte finish, flat maximum 5 units maximum 10 units
Gloss Level 2 a high side sheen flat, a velvet-like finish maximum 10 units 10-35 units
Gloss Level 3 a traditional eggshell- like finish 10-25 units 10-35 units
Gloss Level 4 a satin-like finish 25-35 units minimum 35 units
Gloss Level 5a traditional
semi-gloss35-70 units
Gloss Level 6 a traditional gloss 70-85 units
Gloss Level 7 a high gloss more than 85 units
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W3-W
1
Solid content of paint in % = X 100W
2-W
1
Gloss Measurement
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Gloss meter is essential where an aesthetic appearance of the coating finish is required
and to ensure uniformity of the surface finish. The gloss value is determined by directing a light,
which has a similar wavelength to the human eye, at the test surface and measuring the amount
of specular reflection. Gloss is measured with angles of 60 and 20. The 60 angle is universal
for all applications. The 20 angle gives improved differentiation of measurement on high-gloss
coatings above 70 gloss units. For gloss measurement, the equipment requires is Gardner Gloss
meter. Primary working standard may be highly polished black surface, secondary standard shall
be of material having hard uniform surface such as ceramic tile, secondary standards must be
calibrated against primary standards on a gloss meter conforming to the geometric requirement
of this methods.
3.3.4. Opacity / Hiding Power and Spreading area
Opacity and hiding power measurement was done using quadruplex film applicator. It act
as Multifunctional film applicator with 4 application sides for applying paint-films of 4 different
pre-defined thicknesses, in film width 60 or 80 mm. One side of the applicator is supplied with a
removable guidance support for straight application. Applicators typically consist of a stainless
steel metal bar containing a gap of known depth or clearance on one or more faces. It is placed
near one end of a flat panel, like a test chart. A sufficient volume of paint/liquid is placed in front
of the applicator. The applicator is then "drawn down" the chart, either automatically or
manually, leaving a uniform film behind it.
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Figure: 3.3.4.a Multifunctional film applicator
with 8 pre-defined thickness sides for applyingpaint-films of: 25, 50, 75, 100, 125, 150, 175,
200 micron.
Figure: 3.3.4.b Multifunctional film
applicator with 4 pre-defined thickness sidesfor applying paint-films of: 50,100,150,200
micron.
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In this method the test chart weight was noted and placed 1gram of paint on it in
determined height fixed the chart on glass table. The paint was draw down by using film
applicator of 150micron thickness; again weight of the chart was noted and allowed to dry. The
weight difference of paint indicated the removal of paint during draw down method. This method
was used to identify the opacity property of paint and spreading area for the particular amount of
paint. The spreading area was calculated by graph method.
3.3.5 Drying time
During the drying of alkyd paints different stages were crossed. The first process is the
physical drying of the paint. In this process, the solvent evaporates and a closed film forms
through coalescence of the binder particles. Then chemical drying (also called oxidative drying)
occurs, a lipid autoxidation process, which means that the paint dries by oxidation of the binder
compound with molecular oxygen from the air. During the drying process
four overlapping phases can be discriminated:
Induction period
Hydroperoxide formation
Hydroperoxide decomposition into free radicals
Polymerisation / crosslinking
The induction period is the time between application of the paint to a surface and the start of
dioxygen uptake by the paint film. The induction period occurs because the effects of solvent,
anti-skinning agent and natural anti-oxidants that may be present in the alkyd resin must be
overcome before the drying process can begin. Autoxidation of the unsaturated fatty-acid chains
in the alkyd binder then gives rise to hydroperoxides with uptake of atmospheric oxygen.
Decomposition of these hydroperoxides results in the formation of peroxide and alkoxide
radicals. These radicals initiate the polymerisation of the unsaturated molecules of the bindingmedium. Polymerisation occurs through radical termination reactions forming cross-links,
causing gelling of the film, which is followed by drying and hardening. The number of cross-
linked sites that are formed determines the film hardness. Cross-link formation is irreversible;
hence when a paint layer has dried it.
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CHAPTER 4
CHARACTERIZATION TECHNIQUES USED
4.1 X-RAY DIFFRACTION
X-ray powder diffraction is a method used to determine the crystal structure and analyses
the phase of a particular material. Diffraction occurs as waves interact with a regular structure
whose repeat distance is about the same as the wavelength. X-rays have wavelengths on the
order of a few angstroms, the same as typical interatomic distances in crystalline solids, which
mean X-rays can be diffracted from minerals that, by definition, are crystalline and have
regularly repeating atomic structures. When certain geometric requirements are met, X-rays
scattered from a crystalline solid can constructively interfere, producing a diffracted beam, A
diffraction pattern appears, and this diffraction pattern can be analyzed to determine various
structural properties of a material. Bragg recognized a predictable relationship among several
factors:
1) The distance between similar atomic planes in a mineral (interatomic spacing) called
the d-spacing and measured in angstroms.
2) The angle of diffraction called the theta angle and measured in degrees. For
geometrical reasons the diffractometer measures an angle twice that of the angle 2.
3) The wave length of the incident X-radiation, Symbolized by and measured in
angstroms (equals 1.54 A for copper, which is commonly used).
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Figure: 4.1 Braggs reflection-The principle behind XRD.
These relationships are expressed in an equation defining Braggs law and can be written
as follows
n = 2d sin
Where is the angle of incidence or the Bragg angle and n is an integer number which is
customarily set to one. Now it is possible to determine the d-spacing of the crystal by measuring
the angle at which the intensity is maximized. The mean crystallite size can be calculated by the
Debye-Scherer equation.
Debye-Scherrer equation:
K
D= --------------------
cos
Where
D = Crystallite Size
K = Crystallite Shape factor=0.9
= X-ray wavelength, 1.5418 A for CuK
= Observed peak angle in degree
= X-ray diffraction broadening in radian
Here the instrument used is XPERT- PRO x-ray diffracto meter using CuK Radiation
(wavelength = 1.54016 A) at 40 keV over the range of 2=20- 80.
4.2 ATOMIC FORCE MICOSCOPY (AFM)
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The AFM is an instrument capable of imaging the topography of a given sample. A Nano
sized tip attached on a cantilever is traced over the sample and a 3D image of the sample
topography is generated on a computer. The advantage of the AFM over SEM is the ability to
make topographical measurements for detection and investigation of the size and shape of silver
nano particles in three dimensions at ambient condition. Thus, the AFM makes it possible to
determine the height of the particles also. The present studies were performed using XE 70,
SPM, Park Systems with a scan size of 20 m.
Figure: 4.2 Schematic representation of AFM
The AFM tip is held at the end of a thin, flexible beam, or "cantilever". This cantilever is
made just as the tip was, but its shape is usually triangular ("V" shaped) or long and rectangular
(an "I" beam). These are roughly 100 microns long (which is 0.1 millimeters, about the width ofa hair) and only a few microns thick. This makes them very flexible but strong enough to
securely hold the tips on their end.
Contact mode
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The first and foremost mode of operation, contact mode is widely used. As the tip is
raster-scanned across the surface, it is deflected as it moves over the surface corrugation. In
constant force mode, the tip is constantly adjusted to maintain a constant deflection, and
therefore constant height above the surface. It is this adjustment that is displayed as data.
However, the ability to track the surface in this manner is limited by the feedback circuit.
Sometimes the tip is allowed to scan without this adjustment, and one measures only the
deflection. This is useful for small, high-speed atomic resolution scans, and is known as variable-
deflection mode.
Noncontact mode
Noncontact mode belongs to a family of AC modes, which refers to the use of an
oscillating cantilever. A stiff cantilever is oscillated in the attractive regime, meaning that the tipis quite close to the sample, but not touching it (hence, noncontact). The forces between the tip
and sample are quite low, on the order of pN (10 -12 N). The detection scheme is based on
measuring changes to the resonant frequency or amplitude of the cantilever.
Advantages:
Highest resolution available: AFMs lateral resolution allows imaging and measurement
of features on the order of a few nano meters, the vertical (height) resolution is
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that are emitted after the impact with the specimen, which in turn are used to modulate the
cathode ray tube. Thus an image is formed on the video-display by scanning in synchronization
with the electron beam and a photographic record can be made.
By this technique, materials that are conducting can be imaged. If the conductivity is not
sufficient, it may be coated with conducting layers of gold, carbon etc., before the sample is
mounted in the specimen chamber. The images thus developed may be magnified to the extent of
200K, without any refocusing. It gives more three-dimensional details due to its greater depth of
focus, which is up to about 100 under the lightest voltage conditions (1KV). The main
advantages of SEM are the high lateral resolution (1-10nm) and the numerous types of electron-
specimen interaction that can be used for imaging or chemical analysis. The present studies were
performed on scanning microscopy (SEM) using Hitachi instrument.
Figure: 4.3 working principle of SEM
4.4 FOURIER TRANSFORM INFRA-RED SPECTROSCOPY (FTIR)
The FTIR (Fourier Transform Infrared) spectroscopy deals with the study of the
interaction of matter with Infrared (IR) radiation. FTIR Spectroscopy or simply FTIR Analysis
provides information about the chemical bonding or molecular structure of materials, whether
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organic or inorganic. It is used to identify unknown materials present in a specimen. The
technique works on the fact that bonds and groups of bonds vibrate at characteristic frequencies.
A molecule that is exposed to infrared rays absorbs infrared energy at frequencies which are
characteristic to that molecule. During FTIR analysis, a spot on the specimen is subjected to a
modulated IR beam. The specimens transmittance or absorbance of the infrared rays at different
frequencies is translated into an IR absorption plot consisting of reverse peaks. The resulting
FTIR spectral pattern is then analyzed and mated with known signatures of identified materials
in the FTIR library. The adsorption of radiation by a sample requires that the energy content of
radiation should correspond to the energy difference between the two vibrational states, there
should be strong coupling reaction between the sample and the radiation. This coupling
interaction takes place only if there is a change in dipole moment during the absorption process.
If there is no change in dipole moment during the absorption process, there will be no coupling
interaction between the sample molecules and radiation and therefore no absorption is possible,
even if the first condition is satisfied.
Infrared spectra are usually plotted as percentage transmittance (%T) or absorbance
(A) on a scale, linear in wave numbers (). Transmittance is the ratio of the intensity of radiation
transmitted by the sample (1) to that incident on the sample (I0), expressed as a percentage, so
that T=100(I/ I0) and T and A are related as:
A= log10 (I0/I)
= log10 (100/T)
= 2-log10T
The main advantage of FTIR is the rapid-scan capability, especially for the study of
short-lived species. Nowadays, computer controlled instruments are available which allow rapid
data manipulation, repetitive scanning, signal averaging, background subtraction, spectral
smoothing, fitting & scaling, and searching in digitized spectral libraries & databases, to identify
unknown samples. Among the applications of Infrared Spectroscopy, chemical analysis
(qualitative and quantitative) and the determination of molecular structure are important. The
present studies were performed on an Alpha model FTIR, Brucker, Germany.
4.5 UV-VISIBLE SPECTROSCOPY ANALYSIS
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Absorbance spectroscopy is used to determine the optical properties of a
solution. Light is send through the sample and the percentage of amount of absorbed light is
measured. When the wavelength is varied and the absorbance is measured (wavelength,
absorbance) graph can be drawn using computer software. The applications of this spectroscopy
were extensive. For example, the absorbance can be used to measure the concentration of a
solution by using Beer-Lamberts law. However for examination of nanoparticles, the optical
properties are much more complicated and require an individually developed theory. For
instance, the measured absorbance spectrum does not necessarily show the actual absorbance but
the extinction of light.
The extinction is both the absorbed and scattered light from the particles.
Spectrophotometry is used for both qualitative and quantitative investigations of samples. The
wavelength at the maximum of the absorption band will give information about the structure of
the molecule or ion and the extent of the absorption is proportional with the amount of the
species absorbing the light.
Fig: 4.5 Principle of UV-Visible spectroscopy
The quantitative determinations made by spectrophotometry could be divided in
two groups according to the number of substances to be measured. These are the analytical
measurements of systems that consist of only one absorbing component and systems that consist
of more than one absorbing component. In the case of systems containing one absorbing
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component we measure the absorption of light at a particular wavelength (which is usually
identical with the absorption maximum of the analyte).
We either calculate the concentration from the results by using the molar
absorptivity found in the literature or the unknown concentration can be determined by
comparing the results with a working curve of absorbance versus concentration (calibration
curve) derived using standard
CHAPTER 5
RESULTS AND DISCUSSION
5.1 Iron Oxide nano particle characterization
5.1.1.1FTIR ResultsFigure 5.1.1 shows the IR spectra of iron oxide nano particles. The strong peak found
between 400 and 700 cm-1 is attributed to the vibration band of metal-oxide. The bands at
415,440,473,526 are characteristic vibrations of Fe-O [5].
Figure: 5.1.1 IR spectra for Iron oxide
5.1.2 XRD Analysis
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Figure: 5.1.2 XRD pattern of Iron oxide
The structural feature of iron oxide is explored from XRD data. XRD of iron oxide is
shown in Figure 5.1.2. The XRD pattern of final powders revealed well developed reflections of
iron oxide (JCPDS PDF No. 871164). The XRD pattern of the sample exhibit the characteristic
peak at 2 = 24.5, which corresponds to the (0 1 2) plane. It also exhibits the 2 in 33.5o, 36.07o,
41.32o, 49.85o, 54.51o, 62.83o, 64.4o. The crystalline planes are indexed as (1 0 4), (2 0 1), (2 1 2),
(0 1 5), (0 0 9), (2 3 4) and (2 5 0) as per the JCPDS file no.871164. These peaks showed the
presence of -Fe2O3[6].
5.1.3 AFM studies
Atomic Force Microscopy (AFM) is one of the most powerful tools to study the surface
characteristics of nano phase materials. AFM image of the iron oxide nano particle shown in the
figure 5.1.3. The nano textured structure was well explored by this image and it shows 3D image
of iron oxide. The structural features of the nanoparticles have been explored by the XEI-image
processing software supplied by PARK system, South Korea. The particle size was found to be
around 40 nm.
Figure: 5.1.3 AFM Image of Fe2O3
5.1.4 SEM results
SEM is also used to determine the morphology of the nano particles. Figure 5.1.4
represents the SEM image of iron oxide nano particle. This figure reveals the presence and
uniformly distributed particles. The large particles are composed of small crystallites and show
particle aggregates of irregular shapes and large size. The average size of the particles was found
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to be in the range of 80 nm and undefined shape morphology was observed. Figure 5.1.4 image
was viewed at 3 m scale and 15k magnification at 10kV applied voltage. The SEM images of
this work were obtained using the Scanning Electron Microscope SU1510, Hitachi, Japan.
Figure: 5.1.4 SEM image of Iron oxide
5.2 Characterization of red paint (Iron oxide impregnated)
5.2.1 Composition of red color paint
Table: 4 Iron oxide nano particle impregnated paint
Materials Weight
in gram
Percentage %
Pigment(Fe2O3) 10.00 20.0
Binder(alkyd resin) 30.05 60.1Stabilizer(ZnO) 0.25 0.5Thickener & anti settling agent(Thickener &
Aluminum stearate)
0.50 1.0
Wetting agent(Soya lecithin) 0.25 0.5Inner coat drier(zirconia) 0.25 0.5Upper coat drier(Co. naphthenate) 0.20 0.4Thinner(toluene) 8.50 17.0
Total 50.00 100.0
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Quantity of each constituent present in the paint and its percentage are given in the table
4. Each component was weighed and mixed thoroughly in the ball mill for 1 hour and then the
liquid material was added in it. The ball mill was rotated at 300 rpm for 5 hours. The prepared
red color nano paint was applied on the suitable substrate.
5.2.2 FTIR image for red color nano paint film.
Figure: 5.2.2 IR spectra for iron oxide nano paint film
Figure 5.2.2 shows the IR spectra of iron oxide paint film. The strong peak found
between 400 and 700 cm-1, 1400 to1800 cm-1,1800 to 3000 cm-1 is attributed to the vibration
band of metal-oxide, methyl and methylene groups, linseed oil respectively. The band at 525
represence characteristic vibrations of Fe-O [5]. The band at 1413 cm-1 represence bending
vibration of C-H. The band at 1679, 1739, 3021 cm -1 represence stretching vibration of C=C,
C=O, C-H respectively [7-8].
5.2.3 Comparative study of the red color paint film
a. Corrosion rate and Inhibition efficiency of red color paint
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Prepared red color nano paint was applied on cleaned surface by brush coating method.
For corrosion studies three MS strip was taken such as uncoated, nano paint coated, commercial
paint coated and their weight also noted. Three substrate were separately immersed in 1N HCl
solution. This setup was kept as such as for 24 hours. Then it was removed and dried in air and
its weight was noted. Corrosion rate was calculated based on equation (1). Inhibition efficiency
was calculated based on the equation (2).
Table: 5 CR and IE values of red color paint coated MS plate
MS plate Initial
weight in g
Final weight
in g
Weight loss
in g
Corrosion rate
mg/dm2.day
Inhibition
efficiency %
Uncoated 4.6566 4.4778 0.1788 14.980 -
Nano paintcoated
4.5308 4.5298 1 X 10-03 0.0837 99.4412
Commercialpaint coated 4.6263 4.6230 3.3 X 10
-03
0.2764 98.1528b. Solid content of the red color paint
Solid content of the paint also calculated based on the equation (3).
Table: 6 Solid content of the red color paint
Paint Empty
watch glass
W1 in g
Weight of
watch glass
with paint
W2 (g)
Weight of
specimen
after dry W3(g)
W3-W1in g
W2-W1in g
(W3-W1 ) x 100
W2-W1
Nano paint 36.0389 36.918 36.5845 0.5456 0.8800 62%
Commercialpaint coated 36.0389 37.421 37.1660 1.1271 1.1382 99%
One gram red color paint was poured in the test sheet at a particular point then it was
draw down at 150 micron meter thickness. Same procedure was also followed to the
commercially available red oxide paint. Excess amount of paint was removed during testing. The
testing sheet was allowed to dry completely. Spreading area was calculated by graphical method.
The paint spreaded area was transferred into the graph sheet and area was measured in cm 2.
Gloss @60O was seemed using this sheet. Drying time was also noted.
c. Hiding power and spreading area
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d. Comparative Study between conventional paint and nano formulated red paint
Table: 7 Comparative study of paint property
Test Conventional Paint Nano formulated paint
Gloss @ 60 degree 1 90Solid Content % 99 62%
Hiding Power Background Whitecolor was observed
Good at 150mthickness
Spreading area 46 cm2 70cm2
Corrosion rate in mg/dm2.day 0.2764 0.0837Inhibition efficiency % 98.1528 99.4412Finishing Good Good and shiningRecommended no of coats 2-3 1-2
Drying time at room temperatureDry to touch 30 mins 1-2 hoursDry to handle 2 hour 6 hoursDry to overcoat 6 hours 12 hours
Compared to commercial paint, nano formulated iron oxide paint showed good glossy,
good corrosion resistance. But drying time was high for nano paint.
5.3 Titanium Oxide nano particle characterizations
5.3.1 FTIR Results
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Figure: 5.2.3-a Commercially available Red
oxide paint
Figure: 5.2.3-b Nano formulated Red oxide
paint
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Figure: 5.3.1 IR spectra of titanium dioxide
Figure 5.3.1 shows the IR spectra of titanium dioxide nano particles. The strong peak
found between 400 and 700 cm-1 is attributed to the vibration band of metal-oxide. The band at
549 cm-1 showed the vibrations of Ti-O [9]. The bands at 620 and 726 cm-1 showed the vibrations
of Ti-O-Ti [10].
5.3.2 XRD Analysis
The structural feature of TiO2 is explored from XRD data. XRD of TiO2 is shown in
Figure 5.3.2. The XRD pattern revealed well developed reflections of TiO 2 (JCPDS PDF No.
896975). The XRD pattern of the sample exhibit the characteristic peak at 2 = 25.7, which
corresponds to the (1 0 1) plane. It also exhibits the 2 peaks at 27.8 o, 31.7o, 36.5o, 41.8o, 54.5o &
are indexed as (1 1 0), (2 1 1), (1 0 1), (1 1 1) and (2 1 1) etc. 25.7o
peak showed the differentdiffraction plane of anatase TiO2. 27.8o, 36.5o, 54.5o peaks showed the different diffraction
planes of rutile form of TiO2 [11].
Figure: 5.3.2 XRD Pattern of titanium dioxide
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5.3.3 AFM studies
Figure: 5.3.3 AFM image of titanium Dioxide
AFM image of the titanium dioxide nano particle shown in the figure 5.3.3. The nano
textured structure was well explored by this image. The particle size was found to be around 40nm.
5.3.4 SEM results
Figure 5.3.4 represents the SEM image of TiO2 nano particle. This figure reveals the
presence and uniformly distributed particles. The large particles are composed of small
crystallites and show particle aggregates of irregular shapes and large size. The average size of
the particles was found to be in the range of 90 nm. Figure 5.3.4 image was viewed at 3 m scale
and 17k magnification at 10kV applied voltage.
Figure: 5.3.4 SEM image of Titanium Dioxide
5.4 characterization of white paint (TiO2 based)
5.4.1 Constituent of white based paint
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Table: 8 Titanium dioxide nano particle impregnated paint
Quantity of each constituent present in the paint and its percentage are given in the table
8. Each component was weighed and mixed thoroughly in the ball mill for 1 hour along with
binder. The ball mill was rotated at 300 rpm for 5 hours. The prepared white color nano paint
was applied on the suitable substrate.
5.4.2 FTIR image of white color nano paint film.
Materials Weight in grams Percentage %
Pigment(TiO2) 10.00 20.0
Binder(alkyd resin) 30.00 60.0Stabilizer(ZnO) 0.25 0.5Thickener & anti settling agent(Thickener A
&Aluminum stearate)
0.25 0.5
Wetting agent(Soya lecithin) 0.30 0.6Inner coat drier(zirconia) 0.35 0.7Upper coat drier(Co.naphthenate) 0.35 0.7Thinner(toluene) 8.50 17.0Total 50.00 100.0
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Figure: 5.4.2 IR spectra for titanium dioxide nano paint film
FTIR spectra of TiO2 containing paint film is represented in the figure 5.4.2. It shows all
characteristics peaks corresponding to the linseed alkyd resin at 1413 cm -1 (bending C-H), 1679
cm-1 (stretching C=C), 1739 cm-1(stretching C=O). The stretching (C-H) vibration was observed
from methyl and methylene groups in the range from 2800 to 3000cm -1 and the strong vinyl
stretch vibration =C-H at 3021 cm-1 [7-8]. In addition to these peaks, the characteristic Ti-O
vibrations are found in the region 400-700 cm-1. The peak at 549 and 721 cm-1 are described to
the vibration modes of Ti-O [9].
5.4.3 Comparative study of the white color paint film
a. Corrosion rate (CR) and Inhibition efficiency (IE) for white color paintTable: 9 CR and IE values of white color paint coated mild steel (MS) plate
MS plate Initial
weight in g
Final weight
in g
Weight
loss in g
Corrosion rate
mg/dm2.day
Inhibition
efficiency %
Uncoated 4.6566 4.4778 0.1788 14.980 -
Nano paintcoated
4.5223 4.5039 0.0184 1.5416 89.7089
Commercialpaint coated
4.5506 4.5026 0.048 4.0216 73.1535
Nano paint was applied on cleaned surface by brush coating method. For corrosion studiesthree MS strip was taken such as uncoated, nano white paint coated, commercial white paint
coated and their weight also noted. Three substrate were separately immersed in 1N HCl solution
in different beakers. This setup was kept as such as for 24 hours. The steel substrates were then
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removed and dried in air and its weight was noted. Corrosion rate was calculated based on
equation (1). Inhibition efficiency was calculated based on the equation (2).
b. Solid content of the white color paint
Solid content of the paint was calculated based on the equation (3).
Table: 10 Solid content of the white color paint
Paint Empty
watch glass
W1 (g)
Weight of watch
glass with paint
W2 (g)
Weight of
specimen after
dry W3 (g)
W3-W1(g)
W2-W1 (
g)
100 x (W3-W1 ) /
( W2-W1)
Nano paint 36.0549 37.1253 36.8779 0.823 1.0794 76.2460Commercialpaint coated
43.9502 45.08 44.4958 0.5456 1.1298 48.29
One gram titanium dioxide paint was poured in the test sheet at a particular point then it
was draw down at 150 micron meter thickness. Same procedure was followed to thecommercially available white color paint. Excess amount of paint was removed during testing.
The testing sheet was allowed to dry completely. Spreading area was calculated by graph
method. The paint spreaded area was transferred into the graph sheet and area was measured in
cm2. Gloss @60O was measured using this dried sheet. Drying time was also noted.
c. Hiding power and spreading area
Table: 11 Comparative studies between conventional paint and nano formulated white
paint
Test Conventional Paint Nano formulated paint
Gloss @ 60 degree 3 93Solid Content % 48.29% 76.24%
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Figure: 5.4.3-a Commercially availablewhite color paint
Figure: 5.4.3-b Nano formulated Titaniumdioxide paint
Background Whitecolor was observed
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Hiding Power Background Whitecolor was observed
Good at 150mthickness
Spreading area 94 cm2 86cm2
Corrosion rate in mg/dm2.day 4.0216 1.5416Inhibition efficiency % 73.1535 89.7089
Finishing Poor Good and shiningRecommended no of coats 2-3 1-2Drying time at room temperature
Dry to touch 30 mins 1-2 hoursDry to handle 2 hour 6 hoursDry to overcoat 6 hours 12 hours
Compared to commercial paint, nano formulated titanium dioxide paint showed good
glossy and corrosion resistance. But drying time was high for nano white paint.
5.5 Characterization of prussian blue nanoparticle
5.5.1 FTIR Results
Figure: 5.5.1 IR spectra of prussian blue
Figure 5.5.1 shows the IR spectra of prussian blue (PB) nano particles. The strong peak
found between 500 and 2500cm-1 is attributed to the vibration band of metal-CN links. The peak
at 2080 cm1 is the characteristic CN stretching absorption band of prussian blue and its
analogues, and the absorption band at 501 cm1 is due to the formation of MCNM structures
(M = metal); they indicate the presence of PB [12].
5.5.2 XRD Analysis
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The structural feature of PBis explored from XRD data. XRD of PB is shown in Figure
5.5.2. The XRD pattern of the particles revealed well developed reflections of PB (JCPDS PDF
No. 521907). The XRD pattern of the sample exhibit the characteristic peak at 2 = 17.93,
which corresponds to the (2 0 0) plane. It also exhibits the peaks at 25.3 o, 35.6o, 51.3o indexed as
(2 2 0), (4 0 0) and (4 4 0) planes [13].
Figure: 5.5.2 XRD pattern of Prussian Blue
5.5.3 AFM studies
Figure: 5.5.3 AFM image of PB
AFM image of the PB nano particle shown in the figure 5.5.3. The nano textured
structure is well explored by this image. The particle size was found to be around 120 nm.
5.5.4 SEM results
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Figure 5.5.4 represents the SEM image of prussian bluenano particle. This figure reveals
the presence and uniformly distributed particles. The large particles are composed of small
crystallites and show particle aggregates of irregular shapes and large size. The average size of
the particles was found to be in the range of 90 nm. Image was viewed at 5 m scale and 6.50k
magnification at 10kV applied voltage.
Figure: 5.5.4 SEM image of prussian blue
5.6. Characterization of silver nanoparticle
5.6.1 AFM studies
Figure: 5.6.1 AFM image of silver
AFM image of the Ag nano particle shown in the figure 5.6.1. The nano textured
structure is well explored by this image. The particle size was found to be around 30 nm.
5.6.2. UV-Visible spectrum analysis
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Figure: 5.6.2 UV-Visible spectrum of Ag nanoparticle
Figure 5.6.2 represents the UV-Visible spectrum of Ag nanoparticle prepared by bio-
reduction method using coriander leave extract. The aqueous suspension of the silver
nanoparticle exhibit a peak around 420 nm is a characteristic spectrum of silver nanoparticle in
the UV-Visible spectra [14].
5.7. Characterization of blue color paint film
5.7.1 Composition of prussian blue color paint with Ag and without Ag
Table: 12 property of prussian blue nano particle impregnated paint
Various constituent used for preparing blue color paint is given in the table 12. Each
component was weighed and mixed thoroughly in the ball mill for 1 hour along with binder. The
ball mill grounded the constituents at 300 rpm for 5 hours. The prepared blue color nano paint
was applied on the steel specimen for corrosion studies.
Materials Prussian blue alone Prussian blue with silver
Weight
in gram
Percentage
%
Weight in
gram
Percentage
%
Pigment(Prussian blue) 9.00 18.0 9.00+1.00 20.00
Binder(alkyd resin) 31.10 62.2 30.10 60.20Stabilizer(ZnO) 0.25 0.5 0.25 0.50Thickener & anti settlingagent(Thickener A&Aluminum stearate)
0.30 0.6 0.30 0.60
Wetting agent(Soya lecithin) 0.25 0.5 0.25 0.50Inner coat drier(zirconia) 0.30 0.6 0.30 0.60Upper coatdrier(Co.naphthenate)
0.30 0.6 0.30 0.60
Thinner(toluene) 8.50 17.0 8.50 17.00
Total 50.00 100.0 50.00 100.00
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5.7.2 FTIR image of blue color nano paint film.
Figure: 5.7.2 IR spectra for prussian blue nano paint film
Figure 5.7.2 shows the IR spectra of Prussian blue nano paint film. It shows all
characteristics peaks corresponding to the linseed alkyd resin at 1591 and 1454 cm-1
(Fundamental vibration of Pyrrole ring). The stretching (C-H) vibration is observed from methyl
and methylene groups in the range from 2800 to 3000cm -1 and the strong C-N stretching
vibration at 2071 cm-1.Stretching vibration of C-O-C, C=O is observed at 1255cm -1, 1726 cm-1
respectively. Band at 1120, 1062 cm-1 is observed due to = C-H plane in vibration [7-8]. Band at
738,701 cm-1 is observed due to the C-H out of plane bending vibration. The peak at 519 and 434
cm-1 are described to the vibration modes of M-CN-M [12].
5.7.3 Comparative study of the blue color paint film
a. Corrosion rate and Inhibition efficiency of blue color paint
Prepared blue color nano paint & Prussian blue with silver nano paint was applied on
cleaned surface by brush coating method. For corrosion studies four MS strip was taken such as
uncoated, nano paint coated, nano Prussian blue with silver nano paint, commercial paint coated
and their weight also noted. Four substrate were separately immersed in 1N HCl solution. This
setup was kept as such as for 24 hours. Then it was removed and dried in air and its weight was
noted. Corrosion rate calculated based on equation (1).Inhibition efficiency was calculated basedon the equation (2).
Table: 13 CR and IE values of blue color paint coated MS plate
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MS plate Initial
weight in g
Final weight
in g
Weight
loss in g
Corrosion rate
mg/dm2.day
Inhibition
efficiency %
Uncoated 4.6566 4.4778 0.1788 14.980 -Nano paintcoated
4.5818 4.5681 0.0137 1.1478 92.33
Nanopaintwith silver 4.5349 4.5342 7 X10-4
0.0586 99.61
Commercialpaint coated
4.3577 4.2704 0.0873 7.3142 51.17
b. Solid content of the blue color paint
Solid content of the paint also calculated based on the equation (3).
Table: 14 Solid content of the blue color paint
Paint Empty
watch glassW1 in g
Weight of
watch glasswith paint
W2 (g)
Weight of
specimenafter dry W3(g)
W3-W1
in g
W2-W1
in g
(W3-W1 ) x 100
W2-W1
Nano paint 18.4097 19.5073 19.2393 0.8296 1.0976 75.58Nanopaintwith silver
43.9618 44.9789 44.7058 0.744 1.0082 73.7948
Commercialpaint coated
18.4017 19.4259 18.9372 0.5355 1.0242 52.2847
One gram blue color paint was poured in the test sheet at a particular point then it was
draw down at 150 micron meter thickness. Same procedure followed to the commerciallyavailable blue color paint. Excess amount of paint was removed during testing. The testing sheet
was allowed to dry completely. Spreading area was calculated by graph method. The paint
spreaded area was transferred into the graph sheet and area was measured approximately in terms
of cm2.Gloss @60O was measured using this sheet. Drying time was also noted.
c. Hiding power and spreading area
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d. Comparative Study between conventional paint and nano formulated blue paint
Table: 15 Comparative study of blue paint property
Test Conventional Paint Nano formulated
paint
Nano formulated
paint with Ag
Gloss @ 60 degree 80 85 93Solid Content % 52.2847 75.58 73.7948Hiding Power Good at 150m thickness.
Peeling of material wasobserved if any materialtouches over it.
Good at 150mthickness. Nopeeling of paint film
Good at 150mthickness. Nopeeling of paint film
Spreading area 83 cm2 75cm2 80cm2Corrosion rate 7.3142 mg/dm2.day 1.1478 mg/dm2.day 0.0586 mg/dm2.dayIE % 51.17 92.33 99.61Finishing Good Good and shining Good and shiningAcid resistance Color changes occur No color changes No color changesRecommended noof coats
2-3 1-2 1-2
Drying time at room temperature
Dry to touch 2 mins 1 hours 1 hoursDry to handle 6 hour 3 hours 3 hoursDry to overcoat 12 hours 4 hours 6 hours
Compared to commercial paint, nanoformulated blue paint showed good glossy and
corrosion resistance and drying time was improved.
5.8 Characterization results of Graphene Oxide (GO) nanoparticle
5.8.1 FTIR results
39
Figure 5.7.3-a Commerciallyavailable blue color paint
Figure 5.7.3-b Nanoformulated Blue paint
Figure 5.7.3-c Nano formulatedBlue with silver paint
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Figure: 5.8.1 IR spectra of GO
Figure 5.8.1 shows the IR spectra of Graphene oxide (GO) nano particles. The FTIR
spectrum of GO clearly shows the presence of carboxyl, hydroxyl, epoxyl and carbonyl groups at1728 cm1, 1413 cm1, 1250 cm1 and 1050 cm1 respectively [15]. The peak due to the CC
vibrations from the graphitic domains is observed at 1600 cm1 [16]. The relatively broad peak at
3260 cm1 is due to the adsorbed water content in the surface of GO.
5.8.2 XRD analysis
Figure: 5.8.2 XRD pattern of graphene oxide
The structural feature of GOis explored from XRD data. XRD of GO is shown in Figure
5.8.2. The XRD pattern revealed well developed reflections of GO (JCPDS PDF No. 751621). In
general, the diffraction peak of pure graphite is found around 26 [17]. After successful
oxidation, the diffraction peak of GO shifted towards 2 = 10 which corresponds to the (2 0 0)
plane which is mainly due to the oxidation of graphite and the corresponding interlayer spacing
was 0.85 nm [15,17].
5.8.3 AFM studies
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Figure: 5.8.3 AFM image of GO
AFM image of the GO nano particle shown in the Figure 5.8.3. The nano texturedstructure is well explored by this image. The particle size was found to be around 80 nm.
5.8.4 SEM results
Figure: 5.8.4 SEM image of graphene oxide
Figure represents the SEM image of GO nano particle. The large particles are composed
of small crystallites and show particle aggregates of irregular shapes and large size. The average
size of the particles was found to be in the range of 90 nm and nano sheet shape morphology can
be observed. Figure 5.8.4 image was viewed at 1 m scale and 13000k magnification at 5kV
applied voltage.
5.9. Characterization results of black color paint film
5.9.1 Composition of graphene oxide paint
Table: 16 GO nano particle impregnated paint
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Composition of each component is given in the table 16. Each component was weighed
and mixed thoroughly in the ball mill for 1 hour with linseed alkyd resin. The ball mill wasrotated at 300 rpm for 5 hours. The prepared black color nano paint was applied on the suitable
substrate.
5.9.2 FTIR image of black color nano paint film.
Figure: 5.9.2 IR spectra for graphene oxide nano paint film
Figure 5.9.2 shows the IR spectra of graphene oxide nano paint film. It shows all
characteristics peaks corresponding to the linseed alkyd resin at 1648 cm-1
(Fundamentalvibration of Pyrrole ring) and 1725 cm-1 (C=O stretching vibration) [26-27]. The stretching (C-H)
vibration is observed from methyl and methylene groups in the range from 2800 to 3000 cm -1.
Stretching vibration of C-O-C is observed at 1250 cm-1 [7-8]. Band at 1108, 1054 cm-1 is
observed due to = C-H plane in vibration [15-16].
Materials Weight
in gram
Percentage
%
Pigment(Graphene oxide) 8.00 16.0Binder(alkyd resin) 32.10 64.2Stabilizer(ZnO) 0.25 0.5
Thickener & anti settling agent(Thickener A&Aluminum stearate)
0.27 0.54
Wetting agent(Soya lecithin) 0.28 0.56Inner coat drier(zirconia) 0.30 0.6Upper coat drier(Co.naphthenate) 0.30 0.6Thinner(toluene) 8.50 17.0Total 50.00 100.0
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5.9.3 Comparative study of the black color paint film
a. Corrosion rate and Inhibition efficiency for black color paint
Prepared black color nano paint was applied on cleaned surface by brush coating method.
For corrosion studies three MS strip was taken such as uncoated, nano paint coated, commercial
paint coated and their weight also noted. Three substrate were separately immersed in 1N HCl
solution. This setup was kept as such as for 24 hours. Then it was removed and dried in air and
its weight was noted. Corrosion rate calculated based on equation (1).Inhibition efficiency was
calculated based on the equation (2).
Table: 17 CR and IE values of black color paint coated MS plate
MS plate Initial
weight in g
Final weight
in g
Weight
loss in g
Corrosion rate
mg/dm2.day
Inhibition
efficiency %
Uncoated 4.6566 4.4778 0.1788 14.980 -
Nano paintcoated
4.8734 4.8532 0.0202 1.6924 88.70
Commercialpaint coated
4.9592 4.8741 0.0878 7.3562 50.89
b. Solid content of the black color paint
Solid content of the paint also calculated based on the equation (3).
Table: 18 Solid content of the black color paint
Paint Empty
watch glass
W1 in g
Weight of
watch glass
with paint
W2 (g)
Weight of
specimen
after dry W3(g)
W3-W1in g
W2-W1in g
(W3-W1 ) x 100
W2-W1
Nano paint 36.0289 37.1365 36.7404 0.7115 1.1076 64.24Commercialpaint coated
36.1346 37.1200 36.5210 0.3864 0.9854 39.21
One gram black color paint was poured in the test sheet at a particular point then it was
draw down at 150 micron meter thickness. Same procedure was followed for the commercially
available black color paint. Excess amount of paint was removed during testing. The testing
sheet was allowed to dry completely. Spreading area was calculated by graph method. The paint
spreaded area was transferred into the graph sheet and area was measured f cm2.Gloss @60O was
measured using this sheet. Drying time was also noted.
c. Hiding power and spreading area
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d. Comparative Study between conventional paint and nano formulated GO paint
Table: 19 Comparative study of paint property
Test Conventional Paint Nano formulated
paint
Gloss @ 60 degree 85 75Solid Content % 39.21 64.24Hiding Power Good at 150m thickness. Good at 150m
thickness.
Spreading area 63 cm2 72cm2
Corrosion rate 7.3562 mg/dm2.day 1.6924mg/dm2.dayIE % 50.89 88.70Finishing Good and shining Good and shiningAcid resistance Peel off from the substrate No changesRecommended noof coats
2-3 1-2
Drying time at room temperature
Test Conventional paint Nano formulated
paint
Dry to touch 4hours 1 hoursDry to handle 8 hour 3 hoursDry to overcoat 24 hours 4 hours
Compared to commercial paint nanoformulated black paint showed good glossy and good
corrosion resistance and drying time was improved.
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Figure 5.9.3-b commercially
available black color paint
Figure 5.9.3-a Graphene oxide
black color nanopaint
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SUMMARY
The nanoparticles used for the paint formulation have been prepared by Gel-Combustion
method, mechanical milling method, etc. The prepared nanoparticles have been characterized by
employing XRD, AFM, SEM, FTIR, UV etc. From the analytical parameters, the size of the iron
oxide, titanium dioxide, Prussian blue, Graphene oxide and silver nanoparticles has been
explored in the range of 70, 90, 40, 90, 30 nm respectively. The chemical nature, the metal-
oxygen vibrational modes etc, have been confirmed from the FTIR spectra.
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Nano formulated paint containing nano iron oxide, nano titanium dioxide, nano Prussian
blue, nano Prussian blue with nano silver and graphene oxide have been prepared with other
conventional additives by mechanical milling method. On the application of the prepared paint
over steel structure provides better surface finishes, high glossiness, increasing surface area,
improved hiding power and better corrosion inhibition efficiency compared with commercially
available paints. Compared to conventional paint the drying time was less for nano formulated
paint. Their performance behaviors have also been checked.
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