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The title of the thesis indicates that the work is in connection

with the Polyurethane dispersion coating. Thus it is appropriate
to review coatings and Polyurethane coatings.

1.1 General introduction about Polymer

The word Polymer is frequently addressed to mean a bulky

molecule composed of repeating units, or mers (from the Greek
word meros-part), connected by covalent bonds. Polymers are
indispensible for present mechanized society because of the
resourcefulness of the application. These materials can be
tailored as per longing. However polymer science as a sound
subject is barely few decades old. The demand and importance of
polymers has amplified because of its inherent characteristic such
as light-weight, low cost, excellent chemical resistance, anti
corrosive nature and easy process-ability. Macromolecular science
covers a fascinating field of research, focused on the creation,
the understanding, and the tailoring of materials formed out of
very high-molecular-weight molecules.

To the general public, consumer products like plastics,

fibres, rubber, adhesives, paints, and coatings that all are based
on polymers, and that often the same polymer is used for more
than one application. Until the 1920s and 1930s the several
industries that depend on polymeric materials grew rather
autonomously of one another and were based on natural or
modified natural materials. These industries can be identified in
the broad sense as, Plastics, Rubbers, Fibres, Coatings, and
adhesives [1]. Polymers are classified broadly based on its
applications, origin, and processing. Polymers have versatility of
properties and applications. In the field of Polymers surface
coatings materials have been used for thousands of years in
gradually growing quantities as civilization developed. In the
prehistoric period painting was limited almost entirely to the

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decoration of caves and other dwellings [2]. The ancients applied

coatings to their ships, utensils, musical instruments, weapons,
mummies, temples and palaces. For centuries, surface coatings
were used only for decorative purpose and their preparation and
applications remained more of an art than a science. The
materials used were derived from nature. After the industrial
revolution, the need for protection of metal objects arose. This in
turn slowly transformed the art of paint-making and its
application, into science which gave an impetus to scientists for
making efforts for better understanding of coating compositions,
their constituents, applications and testing. Besides, the
discoveries of new materials and their various applications
constantly pose a challenge for surface coating research in terms
of satisfying increasingly stringent requirements of protection
coupled with decoration in certain instances under diverse service
conditions.

1.2 Types of Surface Coating based on their Function

Surface coatings can be classified into two general types,

convertible (thermosetting) and non-convertible (thermoplastic).
Further classification is possible-particularly with convertible
coatings based on their curing mechanism (air-dry, stoving etc.)
and also based on their performance characteristics (heat
resisting, corrosion resisting, etc.)

A further, very general classification is based on the order

of application, i.e. Based on the methods familiar to professional
decorators, industrial finishers and the general public. In brief
the types are followings.

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1.2.1 High-solids coating

High-solids coatings meet the requirements for

environmentally friendlier coatings, with lower emissions of
organic solvents compared to the conventional alkyd varnishes.

The composition of the binder in oxidatively drying high-

solids alkyd coating systems is partially similar to that of the
binders used in conventional alkyd paints with low solids, the
cross linking process is accelerated by driers. There are,
however, a few characteristic differences that are important for
the drying performance. A part from the higher solids content,
the molecular mass of the binder is also lower and the reactivity
for auto-oxidation cross linking is much higher.

Therefore, to formulate paints with high-solids contents,

low viscosity and acceptable application properties are required.
The high solids content result in thicker applied films, making the
through-drying properties more critical than in low-solids systems
[3].

1.2.2 High build coating

High build coatings are meant for protection by giving a

high dry film thickness in the minimum number of coats. This is
achieved by the incorporation of a gelling agent in the coating
composition, which allows application of thick coats without the
risk of sagging on vertical surface [4].

1.2.3 Solventless coating

Solvent less coating is based on liquid resins of low

viscosity and is used where the presence of solvent is undesirable
e.g. Coatings applied in the interior of tanks. These coatings are
applied on submerged parts of steel and concrete structures.
These paints of high dry film thickness are formulated to cure

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either by chemical reaction (two pack types such as epoxy and

polyurethane) or non-convertible types (e.g. High build
chlorinated rubber) which dry slowly by solvent evaporation [5].

There are several reasons for developing solvent-free and low-

solvent paints: [6]

(1) Reduction of atmospheric pollution

(2) Savings in materials and transportation costs

(3) Savings in energy costs involved in paint production and

use

(4) Time savings due to higher layer thicknesses per application

cycle

(5) Improvement in safety due to low-solvent content.

1.2.4 Water borne coating

Waterborne coatings contain some organic solvent. The

solvents play a variety of important roles in resin manufacture,
coating production, application, and film formation. The two
largest classes of waterborne coatings are water-reducible
coatings and latex coatings, smaller amounts of emulsion
coatings are also used. We use the term water-reducible for
resins made in solvent and reduced with water to form a
dispersion of resin in water. Other resins include aqueous
dispersion resins or water-soluble resins. Some Latex resins are
prepared by emulsion polymerization. Polyurethane latexes are
called aqueous dispersion resins. There is growing use of blends
of different types, for example, combinations of latex and water-
reducible resins.

1.3 Ingredients for formulation of Surface Coating

Today the surface Coatings are designated as paint, water

born, distemper, emulsion, powder coating etc.. All these

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materials have specification which is known as formulation. Such

coating formulation contains mainly pigments, binders, solvents
and additives. The nature and composition of principal groups of
constituents decide ultimate properties of a coating.

A wide range of resins (binders) are commercial available

for surface coating industries now a days but earlier chemist had
to depend on natural product. Very first synthetic resin suitable
for coating material and which is still in use today was phenolic
resin, developed by Leo Backeland in earlier 1900s [7]. After this,
there came the new resin called alkyl in 1923 which is used till
date. After the industrial revolution, extensive research in the
field of polymer chemistry resulted in the availability of numbers
of different resins for suitable for surface coating.

Resin is the continuous phase in a paint films and is largely

responsible for the protective and the general mechanical
properties of the films. A large numbers of resins with different
chemical composition, solubility, nature of film formation,
application characteristics and performance properties of their
films are available for surface coating industries. It is generally
found that the performance properties of a coating systems are
best at higher molecular weight of resin, but it will be difficult to
process high molecular weight during paint manufacturing or
even at the time of paint application whereas at low molecular
weight polymer will facilitate of processing during manufacturing
of a coating system but at the loss of performance properties.

1.3.1Pigments

Pigments are finely divided insoluble solids that are

dispersed in the vehicle and remain suspended in the binder after
film formation. Generally, the primary purpose of pigments is to
provide color and opacity to the coating film [8]. However, there
are many other reasons for the incorporation of pigments into the

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system. Pigments have a considerable influence on the

consistency of the paint and hence on its application properties.
Pigments are also of importance for the resistance of the film to
external attack, in that they are partially responsible for such
properties as resistance to abrasion and weathering. They are
also added for the durability characteristics and to inhibit the
corrosion [9, 10].

Pigments can be inorganic or organic. Inorganic ones are

usually metallic oxides, such as lead oxide, chromium oxide,
cobalt blue etc. Organic ones are generally not found in nature,
and they are synthesized from the coal tar and petroleum
distillates.

1.3.2 Volatile Components (Solvents)

Solvents are used in paints to reduce the viscosity or

consistency of the material and so facilitate the application of a
uniform coating. After application, the solvent is no longer
needed and it should evaporate completely from the film.

Coating solvents, with the exception of water, are volatile organic

liquids. The classes of materials used as solvents include aliphatic
hydrocarbons, aromatic hydrocarbons, alcohols, esters, ketones
and ethers. Water is the solvent in water-borne and emulsion
paints [11].

1.3.3 Additives

In addition to these three components, modern paints may

contain additives of various kinds, such as plasticizers, driers,
emulsifiers or other stabilizers. Additives are the chemical
compounds incorporated in paint in small amounts to improve and
to modify certain desired properties of paint during processing,
storage or during performance of the paint films. They play a
decisive role in the formulation and functioning of a coating [11].

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1.3.4 Binders or resin:

A wide range of resins (binders) are commercial available

for surface coating industries now a days but earlier chemist had
to depend on natural product. Very first synthetic resin suitable
for coating material and which is still in use today was phenolic
resin, developed by Leo Backeland in earlier 1900s [12]. After
this, there came the new resin called alkyl in 1923 which is used
till date. After the industrial revolution, extensive research in the
field of polymer chemistry resulted in the availability of numbers
of different resins for suitable for surface coating.

Resin is the continuous phase in a paint films and is largely

responsible for the protective and the general mechanical
properties of the films. A large numbers of resins with different
chemical composition, solubility, nature of film formation,
application characteristics and performance properties of their
films are available for surface coating industries. It is generally
found that the performance properties of a coating systems are
best at higher molecular weight of resin, but it will be difficult to
process high molecular weight during paint manufacturing or
even at the time of paint application whereas at low molecular
weight polymer will facilitate of processing during manufacturing
of a coating system but at the loss of performance properties
[13-14].

1.3.4.1 Alkyd Resins

Alkyd resins [15-17] form the largest group of the synthetic

resins available to the paint industries and consumption is
greater than that of the any other resin for wide variety of
application due to their low cost and versatility [18-20]. Alkyds
are formed by polycondensation of a dibasic acid and a fatty acid
and in a strict manner alkyds can be defined as oil modified
polyester resin [21]. Most commonly used dibasic acid in alkyd

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synthesis is phthalic anhydride while glycerol,

g lycerol, pentaerythritol,
trimethylol propane, glcols etc. are used as fatty acid determines
the dyeing characteristics of the alkyd resin. Saturated fatty acid
yields non-dyeing
dyeing or plasticizing resin while drying properties are
conferred by unsaturated acids.
ac ids. Alkyds are compatible with most
of the resins used in paint industries like rosin, epoxy, phenolic
resin, amino resin, polyurethanes etc. so it can be easily modified
to achieve specific properties [22].

Alkyd is the most popular in coating industries which find

applications in printing inks, decorative as well as industrial
coating and water soluble and electro deposition systems.

General Structure of Alkyd Resin

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1.3.4.2 Phenolic Resins

The formation of resinous materials by the reaction of

phenol and formaldehyde has been known for many years
[23,24]. Phenolic resin finds application in protective coatings
[25,26]. The reaction of phenol and formaldehyde alone is slow
but in presence of acid different products: Novolacs and Resoles.

OH OH H2 H2
H2 C
C C
Novolac :
OH
OH
CH2

OH

C
H2
OH

OH OH H2
H2 CH2OH
C C
Resole : HOH2C

OH
CH2OH CH2OH
CH2

HOH2C

OH

Novolacs are produced when molar ratio of formaldehyde to

phenol is less than one and acid catalyst is used. Since they are
insoluble in oils and hydrocarbon solvents, they are not used in
surface coating industries but widely used in plastic industries as
a thermoplastic material. Resoles are produced when the molar
ratio of formaldehyde to phenol is greater than one and alkali
catalyst like sodium hydroxide or lime is used. Resoles are

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thermo-setting and soluble in oils so they are used widely in

varnish making but if they are further heated, they react to
produce insoluble and infusible products and result in little
application in surface coating industries.

It is found that resoles react with rosin to give products

which could be esterified with polyhydric alcohols and the
resulting resins are soluble in oils and these resins are known as
rosin modified phenolics which find extensive application in
decorative undercoats, primers, marine paints and in certain
types of printings inks.

1.3.4.3 Polyester Resins

The product obtained from the condensation polymerization

of a polyhydric alcohol and polyfunctional acid is known as
polyester resin [27] and widely used in surface coating industries.
The most commonly used polyfunctional acids are maleic
anhydride, phthalic anhydride, adipic acid, sebasic acid etc.
whereas ethylene glycol, propylene glycol, diethylene glycols are
used as polyhydric alcohols. Depending upon the raw material
used, Polyester can be either saturated polyester or unsaturated
polyester. Both find extensive use in surface coatings [28-32].
Unsaturated polyester are cured by many different ways but the
basic reaction of curing is free radical initiated addition reaction.
Free radical initiation can be achieved either at elevated
temperature by use of an electron beam or UV beam or certain
metal ions as a catalyst by decomposition of peroxides.
Unsaturated polyesters are generally dissolved in reactive solvent
such as styrene to produce final resin and then curing is carried
out. Saturated polyesters are such formulated so that they
produce high hydroxyl contents as they are mainly used in
production of polyurethanes. They also react with some amino
resins.

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1.3.4.4 Epoxy Resins

Epoxy resins [33] are the products of condensation of

epichlorohydrin and diphenylol propane derivative is 2,2’-bis (4-
hydroxyphenyl) propane also known as its trivial name Bisphenol-
A. They are formed by condensing the reactants in presence of
alkali and resulting product is known as diglycidyl ether of
bisphenol-A (DGEBA).

Epoxy resins contain hydroxyl and epoxy groups. They can

be cured by cold curing or stoving with a wide range of materials
which includes amino and phenolic resin, amines, anhydrides,
polyamides and isocynates etc.

The resulting films of epoxy resins are very abrasion

resistant, resistant to chemical attack and show a high degree of
adhesion to metal and other surfaces and thus widely used in
industrial maintenance field [34-36].

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Epoxy Resin

1.3.4.5 Amino Resins

These [37] are derived by reaction between formaldehyde

and either urea or melamine to produce urea formaldehyde or
melamine-formaldehyde respectively. They are not used on their
own as a coating material as they give very brittle films but
widely used in combination with alkyd resins mainly and also with
other resins in co-cure systems.

O O
H2 H H H
C N C N C N C NH
H2

Urea Formaldehyde

Amino resins used in surface coating industries are

generally modified with butanol. The modification of amino resins
with butanol provides solubility in normal coating solvents and

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better compatibility with order resins in co-cure systems.

Melamine formaldehyde shows better properties than urea-
formaldehyde in terms of color retention and exterior durability.

Amino alkyd systems are widely used in staving finishes of

all types. Amino resins are also used with many other resins like
saturated polyester, epoxies, acrylics etc.

1.3.4.6 Polyurethane Resins

The basis of formation of these polymers [38] is reaction

of a diisocyanate with compounds containing an active hydrogen
atom to produce urethane linkages. There are many compounds
that contain active hydrogen like water, alcohol, amines hydroxyl
group etc. Thus a polyurethane film may contain ester, ether,
amide, urea or other groups. The hydroxyl component may be
polymeric polyols like polyesters, polyether etc. Diisocyanates
generally used are tolylene diisocyanates (TDI), isophorone
diisocyanate (IPDI), hexamethylene diisocyanate (HMDI) etc.
Polyurethanes can be either single pack or two pack system.

Polyurethane coating facilities low temperature curing. They

provide wide range of flexibility and hardness. They also process
good adhesion [39] and exhibit excellent weather resistance [40].
Other film properties are good resistance to moisture [41].
Chemical attack [39,42,43] and many solvents [39].

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General Structure of Polyurethane Resin

1.4 General remarks about polyurethane coatings

1.4.1 Urethane chemistry

The polyurethane chemistry is centred on the reactivity of

isocyante groups with compounds carrying labile hydrogen atoms
like hydroxyl or amine functions. The reactions of isocyantes can
be divided into two categories: (1) reactions on reactive
hydrogen to give addition products, for example the reaction
between an isocyante and an alcohol that leads to the formation
of the so-called urethane function, and (2) polymerization of
isocyantes, i.e., self-addition reactions analog to the formation of
dimers (uretdiones) or trimers (isocyanurates). An overview of
basic isocyante reactions is given in Scheme 1.

Aromatic isocyanates are more reactive than aliphatic ones

with decreasing reactivity from primary through secondary to
tertiary isocyanate groups unless steric or catalytic influences
result in reversal reactivity. Primary and secondary alcohols will
react easily at 50-100 °C while tertiary alcohols and phenols will
be slower. The reaction of primary and secondary aliphatic
amines or primary aromatic amines with isocyanates at 0-25 °C
will proceed rapidly. Isocyanates are also very sensitive to water
to yield amine groups. Therefore, PU paint films possess a

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complex polymeric structure with urethane groups but also urea,

biuret or allophanate coupling groups.

The formation of an organic coating usually involves a

liquid phase and generally speaking, two drying mechanisms can
be identified during the formation of the coating paint film:
physical and chemical drying. Physical drying is the evaporation
of the medium where the coating is dissolved or dispersed.
Chemical drying is the formation of the film by means of chemical
reaction. Usually both mechanisms overlap during the formation
of the film. However, a chemical drying which involves the
polyaddition of high and/or small molecular weights starting
products is the most interesting. Two important components can
be identified: oligoisocyanates and co-reactants, usually polyols.

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1.4.2 Isocyanates

The common PU coating formulations are based on few

diisocyanates with aliphatic, cycloaliphatic or aromatic isocyanate
groups. Toluene diisocyanate (TDI), hexamethylene diisocyanate
(HDI), isophorone diisocyanate (IPDI), methylene diphenyl

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diisocynate (MDI) and 1,1-methylenebis(4-isocyanato)cyclohexane

(HMDI) are those of commercial importance (see Scheme 2).
Except MDI and its derivatives, all monomeric diisocyanates are
classified as highly toxic substances and cannot be used into PU
formulations. They have to be converted into higher molar mass
products or prepolymers, physiologically benign polyisocyanates.
For this, urethane chemistry is used in the production of
oligomeric polysiocyanates and permits to obtain oligoisocyanates
with functionalities greater than two, necessary for spatial cross-
linking. Derivatization from diisocyanates is usually performed by
reaction with polyols forming isocyanate-functionalized
urethanes, with water (biurets), with alcohol under catalytic
influence (allophanates) or by catalytic dimerization or
trimerization of diisocyanates (isocyanurates, uretdiones). The
properties of the derivated prepolymers can vary as a function of
molecular weight, type and functionality. For example, aromatic
isocyanates are more reactive than aliphatic ones but their
oxidative and ultraviolet stabilities are lower. They give more
rigid PU but with limited suitability for exterior applications.

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1.4.3 Polyols

Polyols (coreactants) can be polyester, polyether,

polycarbonate or acrylic polymers containing hydroxyl groups
(Scheme 3). The simplest are glycols like ethylene glycol, 1,4-
butanediol or 1,6-hexanediol. The polyol component of the PU
formulation is usually a mixture of those different polymers and
includes sometimes castor oil. The choice of suitable polyols
(architecture, molecular weight…) and oligoisocyanates allows us
to control key characteristics of the paint film like solids content,
gloss, drying, elasticity, hardness or resistance to chemicals. The
ratio of isocyanate to hydroxyl functions (NCO:OH) plays
therefore an important role in the design of the coating film
properties. The use of low molecular weight polyols, for instance,
will result in stiff and hard PU because of the high concentration

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of urethane groups (hard segments). High molecular weight

polyols, on the other hand, will produce more flexible films due
to fewer urethane groups. Polyether polyols are obtained by a
catalyzed addition of ethylene oxide or propylene oxide on small
polyhydroxyl molecules such as ethylene glycol or
trimethylolpropane. Polyester polyols are the result of the
condensation of polyfunctional carboxylic acids (or anhydrides)
with polyfunctional alcohols. Acrylic polyols are produced by free
radical polymerization of 2-hydroxyethyl acrylate or methacrylate
with other alkyl acrylates precursors.

1.4.4 Catalysts

The rates of the different reactions occurring during

hardening of the PU coating film vary and depend on the type of
oligoisocyanates and polyols used but also on the temperature,
on the humidity level, on the catalyst and its nature if one is
used. Most popular catalysts are tertiary amines[45] such as
triethylamine (TEA), 1,4- diazabicyclo[2.2.2]octane (DABCO),

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organotin compounds[46] especially dibutyltin dilaurate (DBTDL)

or stannous octoate (Scheme 4). The catalytic effect of
organometallic compounds is due to their ability to form
complexes with both isocyanates and hydroxyl groups [47, 48]
(Scheme 5). Tertiary amines form a complex with isocyanate
groups which further react with alcohol to form urethane product
[49]. In the absence of a strong catalyst, allophanate and biuret
formation does not take place for aliphatic isocyanates.

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1.5 Polyurethane Coating

Organic coatings or paints on a substrate give aesthetic

desired appearance such as gloss and colour, but also provide
protection against environmental influences like mechanical or
chemical damages, corrosion or radiation.

Discovered in 1937 by Otto Bayer [50], polyurethane (PU or

PUR) raw materials (polyols and polyisocyanates) corresponded,
in 2005, to 1 million tons of the world production of coatings in
industrial applications which totalled 13 million tons. In the
original equipment manufacturer (OEM) automotive coatings
branch, the two-component PUR coating systems almost
completely replaced the traditional alkyd resins especially in large
vehicles production (planes, buses…) where baking of the coating
is not always possible. Indeed, the quality of the PU films dried
under mild conditions matches the performances of the baked
coatings which make PU the ideal system for such application. PU
provide demanded high gloss, colour retention, scratch, corrosion
resistance and the presence of cross-links leads to tensile
strength, good abrasion and mar resistance as well as acid, alkali
and solvent resistance. However, the constant increase in
demands for improved technical performances has motivated
research in both industrial and academic organizations in building
new PU materials with innovative properties. The wide
applicability of PU coatings is due to their versatility in selection
of monomeric materials. Recently, plastic coatings have also
become a further domain for PU among wood furnishing,
corrosion protection or textile coating. The chemistry involved in
the synthesis of PU is centred on the isocyanate reactions.

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 Thermoplastic polyurethane coating

Thermoplastic PU coatings can be qualified as linear

copolymers made up of “soft” and “hard” segments. Hard
segments are composed of polar materials that can form
hydrogen bonds and thus tend to aggregate into hard domains.
Opposite to hard segments, soft segments constitute the
amorphous domains. Such structure was first discovered in 1966
by Cooper et al. [51] where the hard segments play the role of
physical cross-linker to inhibit the motion of soft segments [52].
Hard domains present high glass transition temperature (T g ) and
provide high modulus, tensile strength and dimension stability
while the soft domains with lower Tg impart elastomeric
properties to the material. Therefore, the length of the hard and
soft segments, the sequence of length distribution, the chemical
nature of the units composing the polymer and its molecular
weight are as many parameters that can influence hydrogen
bonding and the subsequent properties of the thermoplastic PU
coating.

 Thermoset polyurethane coating

In thermoset coatings, the presence of high chemical cross-

linking points provides high tensile strength, abrasion resistance
and chemical resistance which are lacking in thermoplastic PU
coatings and are essential for most industrial coatings. Thermoset
polyurethane coatings may contain polyether or polyester as soft
segments with high functionality [53-57], isocyanates with the
functionality greater than two [58, 59], NCO/OH ratios greater
than one [55-57, 60]. The increase in functionality increases
cross-linking concentration which promotes phase mixing [61-64].
And at the other hand, reduces the mobility of the hard segments
[54, 65]. For high performance applications, a calculated amount
of cross-linker is needed to adjust the properties of the PU

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coating. At last, the material, obtained with cross-links

deliberately added or created in-situ, exhibits both phase-
separated and phase-mixed structures, depending on the
concentration of cross-links.

 Moisture cured polyurethane coating

Moisture-cured PU coating contains isocyanate-terminated

pre-polymers and lead to highly cross-linked coatings. The
diffusion and reaction of moisture produces primary amines that
further react into urea groups. The drawback of such coating is
their storage instability. Several side-products such as
allophanate or isocyanurate are usually generated while stored.
The introduction of those additional hard segments changes their
volume fraction within the coating and ultimately alters adhesion
or thermal properties [66-68]. However, moisture scavengers can
be used to improve shelf life and pot stability. On the other hand,
moisture-cured PU coatings produce with superior hardness,
strength and stiffness. Since moisture is consumed, the risk of
blisters or the formation of a weak boundary layer caused by
water trapped under the coating is also greatly reduced.

1.6 Recent Scenario of Coating Technology

Now a day, the trend of using solvent-based paints has

been greatly shifted to the more environmentally friendly
alternatives due to the more severe legislations on environmental
aspects, especially on the emission of volatile organic compounds
(VOC). Because of these concerns and demands, new paint
systems such as water-based coatings, UV and EB radiation
curable coatings, high solids coatings, and powder coatings have
been developed in the last few decades. In order to obtain the
desired performance and to meet legislation requirements, new
proprietary binders, additives and cross-linking technologies such

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as hybrid binders (alkyd-acrylic latexes), organic-inorganic hybrid

systems, tailor made binders[77], telechelic polymers, novel
hyperbranced resins, low surface energy films, new chemistries
for waterborne coating systems, chromate free paints for metal
substrates, tin-free antifouling coatings, and low temperature
curing for powder coatings have been extensively investigated
[69-75].

Today, however, large variety of potential technology

approaches like solid paint, solvent less liquids, energy curing
systems (UV & EB Curable coatings) use of nanotechnology or
combinational- chemistry etc might lead to shifting products and
processes. It is easy to envision a future in which painted metal
might replace asphalt shingles, clay tiles, and other common
roofing materials widely used on residential roofing, and the
automotives industry [76].

In early 1980s, the late Dr.Marco Wismer, one of the

coatings industry’s more visionary members, enunciated “Six
Strategic goals for the coatings industry” as follows which have
never been far from our collective thought in the years since
[77].

1. Corrosion Protection

2. Elimination of Solvents.

3. Conservation of Energy

4. Reduction of Toxic Wastes

5. Cost Reduction

6. Improved durability

Although stated over about almost 2 decade ago, these six

goals are more valid than ever today, and it is clear that the
various global coatings market places, both industrial and

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consumer, are seeking (in some cases struggling) to provide

positive, proactive and economically viable realizations for each
of these goals [77].

In modern age technology and globalization there has been

more emphasis on the painting process and both aesthetics and
protection qualities, along with the high productivity at low cost,
protection of our environment, health & safety is also the biggest
task ahead for the coating technologist.

1.7 Environmental factor need for green coating

technology

Our environment is under attack and there is a potential

threat ahead for earth's water, air, land, animals and human
beings. Every year lots of toxic gases, chemicals and effluents
are being pumped into the environment. This uncontrolled
emission is causing severe damage to our environment and
destroying the ecological balance [78]. Green chemistry
initiatives must be commercially feasible and provide products or
services that have enhanced performance qualities and/or cost
savings in addition to reducing the environmental pollution [79].

For the entire chemical industry, operating sustainable

businesses that provide value–added products and services with
negligible or no environmental impact continues to be zenith
priority. The adoption of a “Green” approach to the
manufacturing and marketing of chemical products, including
paints and coatings, clearly assists companies in attaining this
goal.

Reduction of volatile organic compounds (VOCs) has

been a major focus of the Paint & Coatings industry as
regulations have become increasingly inflexible. The green
chemistry initiatives of many companies have centered on
developing products and processes that reduce or eliminate the

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use of VOCs and the emissions associated with them. Now a day,
“The market for low VOC latexes is growing at an exponential
pace, and is significantly larger than earlier” [80-81].

1.8 Alternative techniques for controlling VOCs

In efforts to lower the VOC emission to reduce risk to

human health, many possibilities in the field of resin chemistry
are being explored by the researchers to develop eco-friendly
organic coating and paint systems.

They are:
1. High Solid Coatings
2. Powder Coatings
3. Radiation Curable Coatings.
4. Waterborne Coatings

The choice of which “compliant” coating is favored in

different applications usually depends upon the cost: performance
ratio for the coating and the expense associated with modifying
existing application facilities to handle the new coating
composition. In various countries throughout the world a variety
of social and economic factors are also known to influence the
acceptance of a new coating technology. For example, in France,
the scarcity of potable water and the abundant availability of
“clean” air readily make high solids coatings more acceptable
than waterborne coatings. On the other hand, the abundant water
supply in Netherlands has caused this country to favor the use of
waterborne coatings. The basic technology involved in these eco-
friendly coating technologies along with their relative merits and
demerits has been well described in the literatures [82, 83, 84].

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Control of VOC by eco-friendly technologies [85]

Sr. %Reduction
Type of Coatings Remark
No. of solvent

Adapted to most
equipment and
1. Waterborne coatings 60-90
low solvent or no
solvent emission.

Viscosity
2. High Solid Coatings 80-90 problem, limited
systems

High cost, need

3. Powder coatings 100
new equipments

High Cost,
4. Radiation Curable coatings 60-90 Limited for flat
surfaces

1.9 Waterborne coatings.

The resins commonly used in conventional solvent borne

coatings are usually modified by increasing their hydrophilic
nature prior to being incorporated into waterborne coating
formulation [85-86]. Most architectural paint and coatings for
cans are based on high molecular weight latexes, with some
being made from water soluble, dispersible, micelle forming
colloids[87]. Typical resin chemistries include acrylics, alkyds,
polyesters, epoxies, vinyl’s and polyurethanes.[86,88,89].
Particularly, polyurethane have found use in wide area of
applications, use in wood coatings, leather industry, aerospace,
and in decorative paints [90].

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 Chapter 1

Recent research and development efforts in waterborne

coatings have been directed towards stabilizing against changes
that occur form induced shear and temperature, improving overall
the performance, and reducing the amount of organic co-solvent
that are required. Improvements in emulsion polymerization, such
that the latex provides its own coalescing properties, and the
development of reactive coalescent are expected to reduce or
eliminate the need for co-solvents [91]. Significance
enhancements in the overall performance of waterborne coatings
have been related to the development of new formulations based
on polyurethane and hybrid polymers, as well as those utilizing
alternative cure chemistry (i.e. UV radiation).

The advantages exhibited by water-bone formulations

include low viscosities, very low VOC content, reduced
flammability, less odor, and easy application using conventional
equipment. The disadvantages associated with these paint and
coatings lie in their cost, their tendency to trap air (e.g. foam)
during high speed application, the capital costs required for
upgrading circulation lines and application equipment to stainless
steel, the ambient temperature storage conditions to
accommodate the freezing point of water, the necessary
pretreatment of many substrates due to the high surface tension
exhibited by water, microbiological degradation, high
conductivity, and the effect that atmospheric humidity and
temperature have on the associated evaporation rates [92,93].

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 Chapter 1

Advantages of waterborne coatings Trade-Sales

Properties Advantages

Easy application Easy brushing and roller coating

Minimal odor Reduced odor during application

Cleanup with water Easy cleanup if done properly

Paint moist surfaces No delay waiting for surfaces to dry out.

Advantages of waterborne coatings – Industrial Area

Properties Advantages

Low flammability Increased worker safety, lower

insurance rates.

Reduced toxicity, odor Increased worker safety,

compliance with occupational
safety and health regulations.

Reduced environmental pollution Eco-friendly environment,

compliance with clean air, and
water legislation

Use of conventional application Save cost of new finishing lines

methods, spray, direct and
reverse roll coater, dip
electrostatic disc or cone

Easily available and wide range Easy of process ability.

of raw materials

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 Chapter 1

1.10 Research Gap

Looking after the present demand of the surface coating

user industries and techno-commercial utility and systematic
literature survey, it reveals that remarkable work was reported on
waterborne polyurethane dispersions since last decade (94-110).
However study on waterborne polyurethane dispersions based on
various polyol such as Polyethylene glycols, alkyd resin and
castor oil (as polyols) has not been found academically and
technically in spite of well defined application of all three
components. Thus the present work is aimed to develop
waterbased ecofriendly coating by using traditional polyol
(polyethylene glygols) and polyols from renewable resources.

1.11 Objectives

In the view of above research gap the objective of present work is

highlighted on

“Synthesis, characterization and coating application of

waterborne polyurethane dispersions derived from various polyols.”

1.12 The Present Work

As per the objective the present PhD work was carried out and the
work is distributed into following four chapters of present thesis.

Several waterborne polyurethane dispersions were synthesized by

using different polyols such as polyethylene glycols, alkyd resin and castor oil,
the aliphatic and aromatic di-isocynates, dimethylol proponic acid as ionic
center and dibutyl tin dilurate as catalyst. By varying the mole ratios of
polyols, di-isocynates and dimethylol proponic acid different waterborne
polyurethane dispersions were synthesized. The route is scanned in Scheme
1.1. The details of these are presented in Chapter 2.

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 Chapter 1

The synthesized Polyurethane dispersions were characterized by IR

spectroscopy, particle size analysis and various physical properties like, color,
appearance, viscosity and self life. The results are discussed in Chapter 3.

Chapter 4 comprises of the film formation of the synthesized

polyurethane dispersions and their characterization. The dispersions were
casted into films and were characterized by physical properties such as drying
time, surface dry, Tack-free dry, hard dry and chemical resistances (alkali and
acid resistance).mechanical study (Tensile strength). The detail about film
casting and data interpretation are furnished in chapter 4.

Thermogravimetric (TGA) and Dynamic Mechanical Analysis (DMA) of

polyurethane dispersion films is carried out. All this data are interpreted in
Chapter 5.

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Scheme 1.1

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