Chapter VII

In this investigation the influence of Nanobarytes, Nanoclay and Nanochalk with respect to
durability performances were studied in polyurethane underlayer coatings. This thesis was dealt
in three stages. They are

Synthesis of polyaniline and Encapsulated Nanochalk, Nanobarytes and Nanoclay

Dispersion of Nanoextenders, Polyaniline and Encapsulated Nanoextenders
Characterisation and durability performances of dispersed Nanoextenders, Polyaniline and
Encapsulated Nanoextenders in polyurethane coatings

Synthesis of polyaniline and Encapsulated Nanochalk, Nanobarytes and Nanoclay:

The challenge is to get required dispersability with Nanoextenders by using conventional

resin medium and process methods. The dispersion is easily achieved for large particles because
adhesion force between pigment particles is small whereas dispersability becomes difficult for
nanoparticles because adhesion force increases rapidly which leads to aggregate formation. In
general, dispersion of Nanoextender is extremely difficult due to its larger surface area particles
and therefore surface of Nanobarytes, Nanoclay and Nanochalk are subjected into modification.
The methods used to disperse them are as follows
o

Encapsulation of Nanoextenders with Polyaniline

Use of Nanosilica solution as wetting and dispersing additive

Firstly, polyaniline was synthesised and then surface modification of Nanobarytes,

Nanoclay and Nanochalk were carried out by PANI encapsulation method. Nanoextenders

were

soaked in Aniline and then, Phosphate doped PANI has been synthesized by chemical oxidation of
aniline with Nanoextenders using ammonium persulfate in phosphoric acid medium. During
encapsulation, Nanochalk (CaCo3) reacts with phosphoric acid (H3PO4) and releases carbon dioxide
(Co2) which results in effervescence. Nanobarytes (BaSo4) and Nanoclay (Al2Si2O5(OH)4) donot show
effervescence unlike Nanochalk.
CaCO3 + 2H3PO 4 Ca(H2PO4)2.H20 +CO2
Calcium Carbonate + Phosphoric acid Calcium di hydrogen phosphate + Carbon dioxide

The synthesized materials such as polyaniline, Encapsulated Nanobarytes, Encapsulated

Nanoclay and Encapsulated Nanochalk were characterised and confirmed using solid state NMR,
SEM, FTIR and DSC. The details are given below

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Chapter VII

Polyaniline

Nodular shaped of PANI particles was confirmed in SEM

Endothermic peak i.e. melting peak absorbed at 40oC which is
confirmed in DSC.
The presence of aniline group was confirmed in FTIR and the peak near
800 cm1 is due to the NH out-of-plane bending absorption.
chemical shifts observed when characterized in

13

C NMR 115 ppm are

assigned to benzenoid protonated carbon resonances of PANI

Encapsulated

Found spherical shaped particle (Nanobarytes) and nodular shaped

Nanobarytes

particles (PANI) was confirmed in SEM

Crystalline domain of Nanobarytes changed during encapsulation
which is confirmed in DSC (shift is from 32oC to 36oC).
In FTIR, the SO42 peaks are slightly shifted to 656 cm_1and 850 cm_1. is
characteristic peak for NH was changed slightly due to encapsulation.
Chemical shifts observed when characterized in

13

C NMR - 120-135

ppm which confirms polyaniline and barytes has no carbon.

Encapsulated

Found platy shaped particle (Nanoclay) and nodular shaped particles

Nanoclay

(PANI) was confirmed in SEM

Crystalline domain of Nanoclay changed during encapsulation which is
confirmed in DSC (shift is from 26oC to 27oC).
In FTIR, peak near 850 cm1 is characteristic peak for NH was changed
slightly due to encapsulation. 500 cm_1 is Si-O-Si and 1400 to 1800
cm_1. is meant for OH group.
Chemical shifts observed when characterized in 13C NMR - 25 - 35 ppm
(sharp peak) and 125- 145 ppm level (broader peak)

Encapsulated

Found nodular shaped particles (Nanochalk and PANI) was confirmed in

Nanochalk

SEM
Crystalline domain of Nanochalk changed during encapsulation which
is confirmed in DSC (shift is from 26oC to 30oC).
In FTIR, peaks at 925 cm_1 which is characteristic peak for NH was
changed slightly due to encapsulation and 1500 cm_1 is characteristic
peak for CO.
Chemical shifts observed when characterized in

13

C NMR: Peaks

observed at 30 ppm, 120 ppm and 220 ppm levels which confirm
presence of carbonates and polyaniline.

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Chapter VII

Dispersion of Nanoextenders, Polyaniline and Encapsulated Nanoextenders:

Polyurethane coatings are leading front by means of providing excellent durability among
resin chemistries used. The following multifunctional groups containing binders were used as
dispersing resin.
Acrylic polyol and Polyester polyol: Both polyols consist of -OH group which forms highly
crosslinked network with Isocyanate resins
Polyvinylbutryate: It is physical drying resin with multi functional reactive groups such as
butyral, acetate and hydroxyl which is expected to give good wetting characteristics with
Nanoextenders

The dispersing resin combination used for the study is Acrylic polyol, Polyester polyol and
Polyvinylbutryate solution in a weight ratio of 19 g / 4.5 g / 5g respectively on total formulation.
The fineness of grind i.e. 10 15 microns was achieved due to the collision of zirconium beads
with the pigment particles and dispersing resin medium. Nanobarytes, Nanoclay and Nanochalk
are dispersed separately at two different concentration levels i.e. 2% and 5% in dispersing resin
medium. The dispersed samples were observed for dispersion stability upto 2 months at room
temperature. There was phase separation and soft settling observed for Nanochalk dispersion
whereas Nanoclay and Nanobarytes dispersion were stable without settling and phase separation.
The synthesized PANI and Encapsulated Nanobarytes, Nanoclay and Nanochalk were
dispersed at two different concentration levels i.e. 2% and 5% in resin medium which contains
acrylic polyol, polyester polyol and poly vinyl butyrate. The dispersed samples were observed for
dispersion stability upto 2 months at room temperature and there were no phase or particle
separation. It is clearly evident that the encapsulation of Nanoextenders is helping to have stable
dispersion even at higher concentration levels. The PANI phosphate encapsulated with
Nanoextenders is intact with multifunctional dispersing medium i.e. Acrylic polyol, polyester
polyol and poly vinyl butyrate.
Nanosilica solution was used as wetting and dispersing additive. The 5% of Nanobarytes,
Nanoclay and Nanochalk are dispersed separately in resin medium which contains acrylic polyol,
polyester polyol and poly vinyl butyrate by using 0.5% Nanoadditive as dispersing additive. The
dispersed samples were observed for dispersion stability upto 2 months at room temperature and
there was no phase or particle separation. Nanosilica solution reduces surface tension between
the resin medium and Nano particles which helps to have stable dispersion.
The dispersion based on Nanoextenders alone, Nanoextenders with Nanoadditive and
encapsulated Nanoextenders are all exhibits stable dispersion. It is clearly evident that the

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presence of Acrylic polyol, Polyester polyol consist of -OH group and Polyvinylbutryate with multi
functional reactive groups such as butyral, acetate and hydroxyl are main reason for stable
dispersion. However, encapsulated Nanoextenders based dispersions are the best among all
other dispersions which proves that polyaniline encapsulation is additional advantage to have
stable dispersion.

Polyvinylbutryate with multi functional reactive groups such as butyral, acetate and hydroxyl

Durability performances:

All 18 dispersions were mixed separately with Isocyanate resin in a weight ratio of 100:30
and applied over mild steel, aluminium substrates. After that, all were top coated with 2K
polyurethane basecoat and clearcoat. The cured film was characterised for surface hardness,
conductivity and elastic properties. Then, the seven days cured film is tested for durability
performances like water resistance, condensed humidity resistance, cyclic corrosion test, neutral
salt spray test and acetic acid spray test.

Influence of Nanobarytes, Nanoclay and Nanochalk:

The tested coating clearly indicates that the incorporation of Nanobarytes, Nanoclay and
Nanochalk reduces the surface hardness. Among the Nanoextenders, the lowest hardness was
observed with Nanochalk followed by Nanobarytes and Nanoclay. Dry adhesion improves
significantly with the use of Nanoclay, Nanobarytes and Nanochalk. The coating film without
Nanoextender showed 15% failure in both substrates whereas no failure was observed with
Nanoextenders. However, further increase in quantity of Nanoclay, Nanobarytes and Nanochalk
from 2% to 5% resulted in similar level i.e. no improvement is observed.
Elastic properties such as impact resistance, conical mandrel, cylindrical mandrel and
Erichsen cupping test resulted in almost similar level with respect to coating without
Nanoextender. However, Nanobarytes showed slightly better flexibility in case of impact
resistance and Erichsen cupping test than Nanoclay and Nanochalk.

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Chapter VII

Water resistance and humidity properties of Nanobarytes (2% & 5%), Nanoclay (2% & 5%)
and Nanochalk (2% & 5%) exhibited no blister tendency and better adhesion was observed even
after 10 days of continuous exposure. However, the condensed humidity resistance of 0%
Nanoextender containing coating showed inferior initial results i.e. finer size denser blisters (8D)
over mild steel whereas there was no blister sensitivity observed over aluminium substrate. And
also, the increase in concentration level of Nanoclay and Nanobarytes showed micro blisters over
mild steel substrates and there are no blisters over aluminum substrates.
Adhesion results under high water spray test were performed as per SAAB (450C and 80
bar pressure) and SCANIA (550C and 120 bar pressure) methods showed that coating without
Nanoextenders showed complete failure. The coating with Nanoclay performs better than
Nanobarytes and Nanochalk due to its plate like structure. The adhesion improves further when
the concentration level increases which proves significance of nanoparticles. Thus, the
incorporation of Nanoextenders improves adhesion properties even under high water spray test.
Cyclic corrosion test after 5 cycles (850hrs) showed that there is no blistering tendency
observed. The corrosion propagation results showed positive improvement with incorporation of
Nanobarytes, Nanoclay and Nanochalk even in lower level (2%) and at higher level (5%). However,
a significant improvement is noticed at 5% concentration level. The minimum corrosion
propagation of 0% Nanoextender is beyond 7mm whereas Nanoextender based coating resulted
in 4-5 mm at 2% concentration level and 2-3 mm at 5% concentration level. This result clearly
ensures that closely packed Nanoextenders has tendency to protect metal from corrosion.
All experimental samples resulted in similar level with respect to blistering (few blisters)
and corrosion propagation when subjected for neutral salt spray test which means that, Nanoclay,
Nanobarytes and Nanochalk addition donot have any adverse effect. A complete delamination is
observed from adhesion promoting Nanocoatings layer to topcoat.
Acetic acid spray corrosion resistance properties over aluminium substrate improved with
Nanoclay, Nanobarytes and Nanochalk. The corrosion level without Nanoextender went up to 20
mm whereas with Nanoextender it reaches maximum upto 2 mm.
Influence of Nanobarytes, Nanoclay and Nanochalk dispersed in Nanoadditive:

The surface hardness of 5% of Nanobarytes, Nanoclay and Nanochalk with Nanoadditive

decreases surface hardness as like previous results. The Surface hardness of 5% Nanobarytes
without Nanoadditive is 227 seconds which reduces to 200 seconds when Nanoadditive is
present. Similarly, surface hardness of Nanoclay and Nanochalk with Nanoadditive reduces to 265
seconds and 143 seconds respectively which were 292 seconds and 159 seconds.

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Chapter VII

Dry adhesion result of Nanobarytes (5%), Nanoclay (5%) and Nanochalk (5%) with
Nanoadditive donot have any negative influence except Nanochalk which showed slightly inferior
initial results. However, all the samples have better adhesion properties after 7days.
Elastic properties such as impact resistance, conical mandrel, cylindrical mandrel and
Erichsen cupping test resulted in almost similar level with respect to coating without
Nanoextender. However, Nanobarytes showed slightly better flexibility in case of impact
resistance and Erichsen cupping test than Nanoclay and Nanochalk.
Water resistance and humidity properties of Nanobarytes (5%), Nanoclay (5%) and
Nanochalk (5%) showed that there is no blister tendency and better adhesion was observed even
after 10 days of continuous exposure. The incorporation of Nanoadditive donot have any negative
influence on blistering and adhesion.
The incorporation of Nanoextender improved adhesion properties and addition of
Nanoadditive doesnt show any negative effect when tested as per SAAB and SCANIA method.
Cyclic corrosion resistance properties showed improvement with incorporation of
Nanobarytes, Nanoclay and Nanochalk. In addition to that, Nanoadditive was used as wetting
additive which could be also present in coating film. The corrosion propagation was tested after
850 hrs which had negative influence i.e. 4-6 mm corrosion when compared to Nanoextenders
without Nanoadditive (2-3 mm corrosion).
Neutral salt spray and acetic acid spray corrosion resistance properties of coatings based
on Nanobarytes, Nanoclay and Nanochalk using Nano wetting and dispersing additive were
resulted in the similar corrosion resistance level. Thus, Nanoadditive inclusion doesnt affect
corrosion resistance properties. A complete delamination is observed from adhesion promoting
Nanocoatings layer to topcoat.

Influence of PANI alone:

The surface hardness, dry adhesion and elastic properties such as impact resistance,
conical mandrel, cylindrical mandrel and Erichsen cupping test showed improvement.
Water resistance and humidity properties of Nanoextenders did not influence blistering
tendency whereas polyaniline is influencing blistering tendency. In particular, blistering tendency
was found to be more especially at higher concentration level of PANI. PANI based coating has
better adhesion over mild steel substrate and inferior initial adhesion losses were found over
aluminium substrate. However, the adhesion loss over aluminium substrate was recovered after
24 hours.
Adhesion results of 2% PANI and 5% PANI based coating under high water spray test
exhibited better adhesion when tested as per SAAB and SCANIA methods. However, 5% PANI
based coating is comparatively better than 2% PANI based coating.

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Chapter VII

In further, 2% polyaniline and 5% polyaniline were also tested for cyclic corrosion
resistance properties. The observed results were revealed that the presence of polyaniline has
remarkable corrosion resistance properties. The minimum and maximum levels of corrosion
propagation were 2 mm and 3-4 mm respectively. This is evidence that use of Nanoextender
resulted in maximum level of corrosion propagation which has gone up to 10-11 mm whereas
with polyaniline alone propagates corrosion only upto 4 mm.
In the VDA cyclic corrosion test, Polyaniline incorporation showed significant corrosion
resistant properties whereas the role is not significant in neutral salt spray resistance. The
delamination behaviour was reduced from complete delamination to 5-10 mm levl. The denser
blistering was observed throughout panel.
Acetic acid corrosion resistance behaviour of coatings based on 2% Polyaniline and 5%
Polyaniline over aluminum substrate remains unaltered. However, the maximum delamination
behaviour (failure from Nanocoatings to topcoat) is observed i.e. from 2 mm to 10 mm for 2%
Polyaniline and 30 mm for 5% Polyaniline.

Influence of Encapsulated Nanoclay, Encapsulated Nanochalk and Encapsulated Nanobarytes in

PANI:
The results of Encapsulated Nanobarytes (2% & 5%), Nanoclay (2% & 5%) and Nanochalk (2%
& 5%) on surface hardness

clearly illustrates

that the

incorporation of encapsulated

Nanoextenders reduces the surface hardness which is very minimal. Among the encapsulated
Nanoextenders, the lowest hardness was observed with Nanobarytes followed by Nanochalk and
Nanoclay. In this, a change in order was noticed in case of encapsulated Nanochalk because the
same resulted in very low surface hardness than others when it was not in encapsulated form.
Dry adhesion results of Encapsulated Nanobarytes (2% & 5%), Nanoclay (2% & 5%) and
Nanochalk (2% & 5%) resulted with 100% intact over mild steel as well as aluminium substrates.
Elastic properties such as impact resistance, conical mandrel, cylindrical mandrel and
Erichsen cupping test resulted in almost similar level with respect to coating without
Nanoextender. However, encapsulated Nanochalk showed slightly better flexibility in case of
impact resistance and Erichsen cupping test than encapsulated Nanoclay and encapsulated
Nanobarytes. Thus, it is clearly evident that synergetic effect of PANI and Nanoextenders helps to
improve flexibility to a greater extent.
Water resistance and humidity properties of Polyaniline alone showed blistering tendency
but it has positive influence when Nanoextenders are encapsulated with polyaniline. But, again it
has negative influence with Nanobarytes at higher concentration level. Adhesion results revealed
that mode of adhesion loss is from adhesion promoting Nano coating to topcoat which is due to
surface smoothness of Nanocoatings. Water penetrates into the adhesion promoting Nanocoating
layer which causes inferior interlayer adhesion due to continuous exposure of coatings in water.

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Chapter VII

In particular, it was bit more in case of aluminium substrates because surface energy is
comparatively lower than mild steel substrate. The size of blistering for Encapsulated
Nanobarytes was smaller whereas bigger size found for Encapsulated Nanoclay and Encapsulated
Nanochalk.
The incorporation of Nanoextenders and PANI alone improved adhesion properties under
high pressure hot water spray test. The synergetic effect of these two resulted in no failure in
case of all the encapsulated Nanobarytes, Nanoclay and Nanochalk i.e. 2% and 5%. However, 2%
encapsulated Nanoclay showed 20% failure. The adhesion of all encapsulated Nanobarytes,
Nanoclay and Nanochalk i.e. 2% and 5% resulted in better adhesion under high pressure hot water
spray test when tested as per SCANIA method. However, 2% encapsulated Nanobarytes showed
100% failure and 2% encapsulated Nanoclay showed 20% failure as like SAAB method.
The cyclic corrosion resistance properties showed improvement with incorporation of
Nanoextenders and further improvement is noticed with polyaniline. The combination of these
two was studied by encapsulating Nanoextenders with polyaniline. The minimum and maximum
level of corrosion propagation was 2-3 mm and 5-6 mm respectively. In particular, corrosion
resistance properties are better at higher level of concentration.
Other corrosion resistance properties such as neutral salt spray and acetic acid spray
resulted in similar corrosion resistance properties. But delamination behaviour was reduced from
complete delamination to maximum to the level of 5 mm in case of neutral salt spray whereas in
acetic acid test it increases especially at higher concentration level.
Thus,

the

durability

performance

of

Nanoclay

i.e.

Hydrated

aluminium

Silicate

(Al2Si2O5(OH)4 is comparatively better than Nanochalk and Nanobarytes due to its platy structure
and presence of SiO2 and AlO6

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Chapter VII

Nanoclays are flat sheets of alternating layers of silicon oxides and aluminum oxides, held
together by ionic attraction for cations sandwiched between the sheets.

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Chapter VII

The durability of Nanochalk (CaCo3) and Nano Barium sulphate (BaSo4) are moderate to good.
Nanochalk easily reacts with acids and forms lot of foaming i.e. evolution of carbon dioxide.

The alkaline metals such as Ca and Ba are strong ionic in nature which is bound together
due to its electrical attraction i.e. opposite charges attract each other. Hence, this type of bonding
is weak and it is soft in nature. Therefore, Nanochalk produces foaming during its encapsulation
i.e. evaluation of carbon dioxide and dispersion also showed aggregates which can be seen in
SEM image. However, Nanobarytes doesnt show any aggregates which gives stable dispersion
and better in most of durability performances.
The closely packed Encapsulated Nanochalk (CaCo3) and Nano Barium sulphate (BaSo4)
enhances durability performances due to presence of Polyaniline. Polyaniline is a catalyst that
mediates the reaction that leads to rust. Polyaniline halts corrosion by accepting electrons from
the metal and in turn, donates them to oxygen creating a two-step reaction that forms a layer of
pure iron oxide. The polymer coating polyaniline is not a heavy metal and does not propose a
threat to human health and it is also cheaper than zinc. Polymers contain conjugated double
bonds or band gaps that allow them to become conductive when doped. Thus, conductive
polymer i.e. polyaniline based coating system showed better corrosion resistance than other
coatings. In addition to that, polyaniline encapsulated Nanoextenders based coating further
showed added performance improvement.

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Chapter VII

Overall, the durability enhanced by polyurethane coatings because Nanoextenders and

encapsulated Nanoextenders dispersed in multifunctional resin system (Acrylic polyol, Polyester
polyol and Polyvinyl butyral) which is cured with Isocyanate resin. This forms highly crosslinked
network and in that nanoparticles are closely packed. All these hybrid system provides improved
performances.

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Chapter VII

Conclusions:
The following conclusions were made

Suitable dispersion techniques for Nanobarytes, Nanoclay and Nanochalk:

The Nanobarytes, Nanoclay and Nanochalk showed stable dispersion when dispersed in
acrylic polyol, polyester polyol and poly vinyl butyrate resin combination. However, among those
dispersions Nanochalk showed soft settling and aggregates which was also seen in SEM analysis
of cured film. The incorporation of Nanoadditive as wetting and dispersing additive also resulted
in similar behaviour of stability. Also, dispersion based on encapsulated Nanoextenders with
polyaniline (PANI) showed very stable dispersion than other dispersions. It proves that synergetic
effect of polyaniline and Nanoextender combination by means of encapsulation provides stable
dispersion. Dispersing binder such as acrylic polyol, polyester polyol and poly vinyl butyrate resin
combination found to be the right choice for dispersing nanoparticles because it has multi
functional groups such as hydroxyl, acetate and butyrate which provide stable dispersion.

Influence of Nanobarytes, Nanoclay and Nanochalk:[with and without Nanoadditive]

Stable dispersion and No agglomerates seen in SEM [analysis done for cured coating film]
for Nanobarytes and Nanoclay
Binder separation and Agglomerates seen in SEM [analysis done for cured coating film] for
Nanochalk

Influence of PANI alone:

Easily dispersed, No binder separation and Stable dispersion
Slight agglomerates seen in SEM [analysis done for cured coating film]
Influence of Encapsulated Nanoclay, Encapsulated Nanochalk and Encapsulated Nanobarytes
in PANI:
Easily dispersed, No binder separation and stable dispersion
No agglomerates seen in SEM [analysis done for cured coating film]

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Chapter VII

Performance of Nanobarytes, Nanoclay and Nanochalk in polyurethane underlayer protective

coatings:

The dispersed Nanobarytes, Nanoclay and Nanochalk were crosslinked with Trimer
Isocyanates and cured polyurethane coatings based panels were tested for durability
performances. The performance of Nanobarytes, Nanoclay and Nanochalk based PU coating was
better in elastic properties, adhesion properties, water and humidity resistance properties. In the
corrosion resistance properties, the delamination of film was resulted which is due to smooth
surface of Nanoparticle based PU coating. The dispersions based on Nanobarytes, Nanoclay and
Nanochalk with Nanoadditive also resulted in similar level as that of without Nanoadditive.
Polyaniline alone based coating showed blistering tendency in water, humidity and
corrosion resistance properties. However, corrosion resistance properties are extremely good.
The dispersions based on Encapsulated Nanobarytes, Encapsulated Nanoclay and Encapsulated
Nanochalk was resulted better in elastic properties, adhesion properties, water resistance,
humidity resistance and corrosion resistance properties. The encapsulation reduces blistering
tendency when compared to polyaniline. Therefore, encapsulation technique is vital for having
stable dispersion as well as to have better durability performances. However, the delamination of
film was resulted when tested for corrosion resistance properties which is due to smooth surface
of Nanoparticle based PU coating. Overall, Nanochalk is slightly inferior especially stability of
dispersion when compared to each other Nanoextenders performance. However, Nanochalk is
better than without Nanoextenders coating performance. The following are details

Characterisation
Pendulum hardness
test To check for
surface roughness

Significant improvement:

Nanochalk > Nanobarytes ~ Nanoclay

Moderate improvement:

Encapsulated

Nanochalk

>

Encapsulated

Nanobarytes

>

Encapsulated Nanoclay
Decrease in roughness:

Adhesion test ASTM

D3359

0% Nanoextender, polyaniline

No failure:

Nanochalk, Nanobarytes, Nanoclay, Polyaniline, Encapsulated

Nanochalk, Encapsulated Nanobarytes, Encapsulated Nanoclay

< 80% failure:

0% Nanoextender

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Chapter VII

Impact

resistance

(flexibility test)

Significant Improvement:

Nanochalk > Nanobarytes, Nanoclay Polyaniline, Encapsulated

Nanochalk, Encapsulated Nanobarytes, Encapsulated Nanoclay

Conical Mandrel (ISO

Improvement: Nanoclay, Encapsulated Nanoclay

6860)

Slightly Inferior:

(flexibility

test)

Nanochalk, Nanobarytes, polyaniline, Encapsulated Nanochalk,

Encapsulated Nanobarytes

Cylindrical flexibility

No failure in cylindrical flexibility test for Nanochalk, Nanobarytes,

test

Nanoclay,

Polyaniline,

Encapsulated

Nanochalk,

Encapsulated

Nanobarytes, Encapsulated Nanoclay

Erichsen

flexibility

test

No improvement:

Nanobarytes, polyaniline, Encapsulated Nanochalk, Encapsulated

Nanobarytes, Encapsulated Nanoclay

Slightly Inferior:

Conductivity

Nanoclay, Nanochalk

Higher Conductivity:

Nanoclay, Nanochalk, Nanobarytes with Nanoadditive, Nanoclay

with

Nanoadditive,

Polyaniline,

Encapsulated

Nanobarytes,

Nanoadditive,

Encapsulated

Encapsulated Nanoclay

Lower in Conductivity:

Nanobarytes,

Nanochalk

with

Nanochalk

Durability performances
Water Resistance

No blistering and No adhesion loss:

[Tested
blistering
adhesion]

for

Nanochalk,

Nanobarytes,

Nanoclay,

Nano

extenders

with

Nanoadditive

and
No blistering and adhesion loss:

Encapsulated Nanochalk, Encapsulated Nanoclay

Denser Blistering and adhesion loss:

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Chapter VII

polyaniline, Encapsulated Nanobarytes

Polyaniline more prone to blistering tendency and it is confirmed that

Nanoextenders alone does not have blisters
Humidity resistance

No blistering and No adhesion loss:

[Tested for

Nanochalk, Nano barytes with Nanoadditive

Micro blistering and adhesion loss:

blistering and

adhesion]

Nanobarytes, Nanoclay, Nanochalk with Nanoadditive, Nanoclay

with Nanoadditive

Denser Blistering and adhesion loss:

polyaniline, Encapsulated Nanobarytes, Encapsulated Nanochalk,

Encapsulated Nanoclay

Polyaniline more prone to blistering tendency and it is confirmed that

Nanoextenders alone does not have denser blisters

Hot water spray test

[Tested for adhesion
properties

No failure:

under

high

pressure

hot

water

Encapsulated Nanobarytes, Encapsulated Nanoclay, Encapsulated

Nanochalk

and
spray

conditions]

Less than 15% failure:

Nanobarytes, Nanoclay, Nanoclay with Nanoadditive, polyaniline

Complete failure:

Nanochalk, Nano barytes with Nanoadditive, Nanochalk with

Nanoadditive

VDA Cyclic corrosion

[corrosion

Remarkable improvement in corrosion resistance:

resistance

Polyaniline, Encapsulated Nanobarytes, Encapsulated Nanoclay,

Encapsulated Nanochalk

properties over Mild

steel substrate]

Improved corrosion resistance:

Nanobarytes,

Nanoclay,

Nanochalk,

Nanoextenders

with

Nanochalk,

Nanoextenders

with

Nanoadditive

Neutral salt spray

test [corrosion
resistance

Improved corrosion resistance:

Nanobarytes,
Nanoadditive,

Nanoclay,

Polyaniline,

Encapsulated

Nanobarytes,

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Chapter VII

properties over Mild

Encapsulated Nanoclay, Encapsulated Nanochalk

steel substrate]
Less than 10 mm delamination:

Polyaniline, Encapsulated Nanobarytes, Encapsulated Nanoclay,

Encapsulated Nanochalk

Complete Delamination:

Nanobarytes,

Nanoclay,

Nanochalk,

Nanoextenders

with

Nanochalk,

Nanoextenders

with

Nanoadditive

Acetic

acid

spray

test

Improved corrosion resistance:

Nanobarytes,

Nanoclay,

[corrosion

Nanoadditive,

resistance

Encapsulated Nanoclay, Encapsulated Nanochalk

properties
Aluminium
substrate]

Polyaniline,

Encapsulated

Nanobarytes,

over
Less than 10 mm delamination:

Nanobarytes,

Nanoclay,

Nanochalk,

Nanoextenders

with

Nanoadditive

Less than 20 mm delamination:

Encapsulated Nanobarytes, Encapsulated Nanoclay, Encapsulated

Nanochalk

Less than 30 mm delamination:

Polyaniline

The delamination is from Nanocoating to topcoat which clearly indicates that surface
smoothness. Nanoextenders alone resulted in lesser delamination and polyaniline alone lead to
more delamination which in turn reduced after encapsulation. Therefore, delamination can be
reduced by addition of Nanoextenders at right optimised quantity.

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Chapter VII

The following are summarised conclusions

Stable dispersion found in encapsulation of Nanoextenders with polyaniline (PANI)
Dispersing binder such as acrylic polyol, polyester polyol and poly vinyl butyrate resin
combination found to be the right choice for dispersing nanoparticles
Dispersing binder with multi functional groups such as hydroxyl, acetate and butyrate
provides stable dispersion.
Nanoextenders alone based coatings better in elastic properties, water and humidity
resistance whereas it has moderate corrosion resistance properties
Polyaniline alone based coating showed blistering tendency in water and humidity
resistance properties and corrosion resistance properties. However, corrosion resistance
properties are extremely good.
Coatings based on Encapsulated Nanobarytes, Encapsulated Nanoclay and Encapsulated
Nanochalk were resulted in better for elastic properties, adhesion properties, water and
humidity resistance properties and corrosion resistance properties.
Encapsulation reduces blistering tendency compared to polyaniline and it has stable
dispersion and better in durability performances.
The presence of PANI Phosphate is creating synergetic effect and its main function is as
follows

PANI: It is conducting polymer which resists corrosion propagation

Phosphoric acid medium: It etches the metal substrates thereby it provides

better interlayer adhesion

Nanoextenders: Closely packed atoms which can act as barrier layer

Recommendations:
Following are the recommendations from this investigation
To reduce delamination behaviour of nanoparticles, pigment volume concentration of
Nanoparticle based coatings need to be optimised. Thereby porosity of film varies which
helps to have better interlayer adhesion properties.
Polyurethane underlayer coatings based on Encapsulated Nanoparticles showed significant
improvement in durability. However, extensive study is needed to be performed to have
similar or better performance as that of chromate containing adhesion promoting layer
Encapsulation of Nanochalk is to be optimised due to its high exothermic nature. It can be
useful to reduce aggregates.

236

Chapter VII

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