Material & Metalurgi

Organic Coating
 Life time of coating: Role of corrosion – resistant
coating

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 Organic coating
• A barrier action from the layer or active corrosion inhibition
→ provided by pigments in the coating.
• Limited barrier → because of permeable to water and
oxygen.

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 The corrosion mechanism in organic coating
• The total corrosion process takes place as follows:
• Migration through the coating of water, oxygen, and ions
• Development of an aqueous phase at the coating/substrate
interface
• Activation of the substrate surface for the anodic and cathodic
reactions
• Deterioration of the coating/substrate interfacial bond

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 Material & Metalurgi

Principle of coating
 Two primary sciences of liquid flow and solid–
liquid interaction
• Rheology
• Rheology deals with the flow and deformation of the liquid
(viscosity)
• Surface chemistry
• Surface chemistry, involves the attractive forces liquid molecules
have for each other and for the substrate.

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 Rheology
• Rheology, the science of flow and deformation, is necessary to
the understanding of coating use, application, and quality
control.
• The key rheological property of coatings is viscosity, which is
simply the resistance of a coating to flow, the ratio of shear
stress to shear rate.

• Thin or low-viscosity liquids flow easily while high-viscosity

liquids move with considerable resistance.

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 Surface chemistry
• To understanding interaction the interfacial reactions of
coating materials:
• To analyze the liquid–solid interaction.
• The effect of surface interaction between a liquid coating and the
surrounding air is small and can be ignored.

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 Surface chemistry
• Surface tension
• Surface tension is one of the factors that determines the ability of a coating to
wet and adhere to the substrate. All liquids are composed of molecules, which
when close to one another exert attractive forces. It is these mutual
attractions that produce the property called surface tension.
• The units are dynes per centimeter (force per unit length).
• Wetting
• The ability of a liquid to wet a surface is related to its surface tension.
• Using solvents with lower surface tension, one can improved the ability of a
coating to wet a substrate.
• The angle that the drop or edge of the liquid makes with the solid substrate is
called the contact angle θ. The smaller the contact angle, the better the
wetting

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 Surface chemistry
• Coalescence
• Coalescence is the fusing of molten particles to form a continuous film.
Surface tension, radius of curvature, and the viscosity of the molten
powder control coalescence. To have more time available for leveling, it
is desirable to have small particles, low viscosity, and low surface
tension.
• Surfactants
• A substance that tends to reduce the surface tension of a liquid in
which it is dissolved
• Surfactants are also known as wetting agents. They are used to lower
the surface tension of coatings and paints.
• Surfactants possess two different chemical groups, one compatible with
the liquid to be modified and the other having a lower surface tension.

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 Wetting

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 Material & Metalurgi

Theory of adhesion
“The coating’s resistance to weather, chemicals,
scratches, impact, or stress is only of value while the
coating remains on the substrate”
 Adhesion
• The adhesive is said to “wet” the surface. If the tape is
applied to clear glass and the attached area viewed through
the glass, it will be noted that in certain areas the
adhesive/glass interface appears like a liquid/glass interface.
• Adhesion is a complex phenomenon related to the physical
effects and chemical reactions at the “interface.”
• The actual mechanism by which adhesion occurs is not fully
understood.

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 Adhesion
• Several theories have been proposed to explain the
phenomenon of adhesion, including
• Mechanical bonding
• Electrostatic attraction
• True chemical bonding
• True paint diffusion.

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 Mechanical bonding
• The bonding → When a substrate surface contains pores,
holes, crevices, and voids into which the coating spreads and
solidifies, a mechanical bond is formed.
• Effect of mechanical bonding → The removal of the coating
is made more difficult if the substrate has undercut areas
that are filled with cured coating.

Mechanical interlocking
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 Mechanical bonding
• The adhesion of a coating is improved by surface roughness.
• Instrumental analyses have indicated that a coating can
penetrate to complex tunnel-shaped undercuts and cracks
where, upon curing to a hard mass, a mechanical
attachment results.

Does high surface roughness always cause good adhesion?

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 Surface profile related to mechanical interlocking

Poor adhesion

Good adhesion
Marginal wetting and trapped air in
the depression

The advantage of surface roughness is realized only if the coating

penetrates completely into all surface irregularities.
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 Electrostatic attraction
• Electrostatic forces → An electrical double layer at the
coating/surface interface.
• Both coatings and surfaces contain electrical charges spread
throughout the system.
• Interaction between these charges could be responsible for
some adhesion. Much of the attraction between coating and
surface is provided by these charges. Such interactions are only
effective over a very short range.
• Because these forces are not significant beyond about 0.5 mm,
the need for intimate contact between coating and surface
becomes obvious.

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 Chemical bonding

• The formation of chemical bonds

across the interface very likely
takes place in thermoset coatings.
• Such bonding is expected to be
the strongest and the most
durable.
• For this to occur, it is necessary
for mutually reactive chemical
groups to be tightly bound on the
substrate surface and in the
coating.

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 Chemical bonding
• Organo-silanes → to promote adhesion between
the resin and the glass in fiberglass-reinforced
plastics.
• Silanol groups + the silanol groups (on the glass
surface or possibly with other metal oxide groups)
→ to form strong ether linkages.
• The super adhesion of melamine-cured acrylic
topcoats over polyester/ melamine-cured primers
(surfaces) is the result of coatings containing
reactive functional groups such as hydroxyl or
carboxyl moieties over substrates containing
similar groups.
• When a substrate contains reactive hydroxyl Reaction to two-components
groups that can react with diisocyanate groups polyurethane with a reactive surface
contained in thermoset polyurethane coatings,
chemical bonding also takes place ( Figure).

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 Paint diffusion
• When two phases of coating and polymeric substrate attain
molecular contact by wetting, segments of the
macromolecules will diffuse across the interface. The extent
of the migration will depend on the material properties and
curing conditions.
• Auto adhesion process:
• Wetting followed by diffusion of chain segments across the
interface to re-establish the entangled network.
• Dissimilar polymers are usually incompatible because of their
long-chain nature and low diffusion coefficients.

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 Adhesion test
• Because a specification for the degree of adhesion must be
provided in almost every paint formulation, methods for
routine measurement of that key quantity have been
established.
• The two primary test procedures are:
• The cross-cut test
• Pull-off methods

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 Cross – cut
• The standard: ASTM D-3359 (Tape test) → common used method
• Method →
• Version A: An X cut is made in the film to the substrate, and pressure-sensitive tape
is applied over the cut and then removed at an angle close to 180 ° . The adhesion is
assessed qualitatively on a 0 to 5 scale.
• In version B, a lattice pattern is cut to the substrate using a multiple cutting tool
consisting of a set of six or eleven “knives” 1 or 2 mm apart in each direction
(Figure). Pressure-sensitive tape is applied over the lattice and then removed.
Adhesion is evaluated by comparison with description and illustrations.
• The classification is based on estimating the amount of paint flakes separated
from the substrate. The ISO recommends standard considering the test for
“go/no-go” statements. In such a case, class 0 would indicate perfect adhesion
whereas class 2 or even class 1 should be interpreted as an objectionable
result.

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 Cross-cut test paint film classification

• The classification is based on estimating the amount of paint flakes separated from the substrate.
• The ISO recommends standard considering the test for “go/no-go” statements. In such a case,
class 0 would indicate perfect adhesion whereas class 2 or even class 1 should be interpreted as
an objectionable result.

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 The advantages and disadvantages of the tape
test
• Advantages
• being simple and economical to perform and lends itself to job site
application.
• Disadvantages
• Poor reproducibility and high subjectivity.
• The test actually measures the quality of adhesion between the coating
and the tacky adhesive on the tape. A less tacky tape can produce
erroneous results.
• The tape test is operator sensitive, the burden of accuracy and
reproducibility depends on the skill of the operator. Key steps that
directly reflect the importance of operator skill include the visual
assessment of the tested sample and the angle and rate of tape
removal.

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 Tensile method
• The pull-off method has been standardized internationally.
• ASTM Test Method D-5179 is for measuring adhesion of organic
coatings to substrates.
• ISO 4624 is a similar pull-off test. In either case, a metallic stud (either
aluminum or steel) is glued with the coating to the substrate and is
subjected to axial tension until detachment of the paint film occurs.
• The adhesion strength is the maximum tensile stress possible at
the interface.
• Adhesive strength is affected by the coating thickness and the
solvent retention when solvents containing coatings are used.

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 Tensile method
• When a torque is applied about the axis or the stud, the process of
detachment indicates the maximum shear stress that can be attained at
the interface. This is also a measure of adhesion.
• The values of adhesion strength obtained from both methods are of the
same order of magnitude. However, there is a tendency to obtain
results with the torque principle in the case of cohesive failure, but
lower results for adhesive failure (Figure).
• It is important that an appropriate adhesive be used to firmly attach the
stud to the test area. In general, the fast-hardening cyanoacrylates or
the solventless epoxy resin adhesives cured with polyamines can be
used for this purpose. The constituents of the adhesive must not
interact with the coating in a manner that causes complete swelling.

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 Determination of adhesive strength

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 Effect of coating thickness on bonding strength

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 Indentation de-bonding
• Process of indentation
• A needle-like indenter is pressed perpendicularly into the surface of a
coating that is bonded to a virtually undeformable substrate.
• A 60 °angle cone has proven optimal for taking into account boundary
conditions at the interface.
• Most of the deformation will take place within the film, but there will
also be some debonding at the interface.
• Optical devices can be used to monitor the gradually increasing
area of debonding, especially on thin coatings
• A particular advantage of the indentation test is that it yields
values for bond strength in absolute terms, as well as
information about the durability of the bond between the
coating and substrate.

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 Principle of the indentation process

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 Impact test
• An impact test is used to determine the stone-chip resistance of a coating.
The value of adhesion at the interface is of primary concern.
• A steel ball impinging on the test piece can duplicate the situation
encountered in actual practice.
• As a first approximation, the transfer of forces through the film is equal to the
case of static loading, and can be calculated in essentially the same way as for
an indentation test.
• In the debonding area, negative tensile (compressive) stress is present in the
center of the detachment site and sheer stress is present in the annular
region.
• The maximum diameter of the bonding area can serve as a measure of
adhesion at the interface. The diameter, and better yet the area of the
debonding zone, both serve as (reciprocal) measures of adhesion. An
extended debonded site is an indication of a low adhesion level.

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 Impact effect on interface adhesion

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 Delamination test
• In the previous tests, the primary concern was stress
conditions at the interface.
• Delamination is the result of peeling forces that attack the
bond between the paint film and substrate.
• The attack occurs either at well-defined lines, so that the
coating is detached in strips, or at one point only, causing
delamination to progress rapidly in the form of a blister. Both
conditions occur in practice.

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 Delamination test
• Three types of tests have been developed to test for
delamination.
• Knife cutting method
• Peel test
• Blister method

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 Knife cutting method
• Testing process
• Film separation is obtained by means of a sharp knife pushed along the
interface with a measured force.
• The process of detachment comprises both tensile and shear stresses,
which eventually cause detachment of the film.
• Analysis → It is determined by:
• The rake angle of the knife, coating thickness, friction between the
cutting tool and coating as well as substrate, amount of energy
elastically in the film and energy losses caused by plastic deformation,
fracture energy occurring during decomposition within the film, and
other effects of lesser importance.
• All these factors must be either strictly controlled or their influence
estimated as accurately as possible.

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 Influence of mechanical paint film properties on
the results of knife cut test

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 Peel test
• Testing process
• To conduct the test, a strip of sufficient width is marked on the sample by two parallel cuts of
adequate length.
• a coating fails due gradual peeling either from a sparsely covered edge or from a line-shaped
damaged area.
• Analysis
• Detachment of the film is the result of the combined effects of both positive and negative
tensile stresses and shear stress.
• The details of the separation process are quite complicated, although at first glance the
process might appear relatively simple.
• The viscoelastic nature of the film is a contributing factor and this property is also affected by
the amount of pigmentation in the film.
• Because of the viscoelasticity of the film, the test results also depend on the velocity of the
detachment process.
• Although the peel test is a practical method, the results cannot be interpreted in terms
of the bonding mechanism.

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 Devices for measuring adhesion on the basis of
delamination

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 Blister method
• Background
• The first indication that a coating designed for protection against
corrosion is deteriorating occurs when a blister forms.
• The following test has been developed to investigate this type of
failure.
• Process
• A hole is bored into the substrate prior to applying the paint
coating.
• The hole is plugged with a non wetting material such as Teflon.
• This will permit easy removal of the plug after the substrate has
been painted.

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 Blister method
• Process
• Hydrostatic pressure is applied in the hole, either with a fluid (oil,
mercury, etc.) or with pressurized air.
• The pressure is the primary measure of the debonding process.
• The height and diameter of the blister are measured to obtain the
maximum stress or bonding energy (work of adhesion).
• From this geometrical data, together with the tensile modulus of the
film and its thickness, a critical pressure value can be calculated:
• It is this process that causes the blister to grow; therefore, this pressure
serves as the basis for determining the adhesive strength W = 0.65Pd

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 Test for measuring adhesion based on blister
dimension

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 Flaw detection method
• Background
• Once a coating has been applied, and throughout its lifetime, it is
necessary to determine any deterioration of the bonding strength
between the film and the substrate.
• These tests provide a means of detecting the first signs of
adhesion failure. The nondestructive measurement of adhesion
quality has gained popularity in recent years.
• Extensive work has been successfully applied to the general rise
in nondestructive methods to predict adhesive bond quality.
• Ultrasonic pulse echo system
• Thermographic detection
• Acoustic emission analysis

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 Ultrasonic pulse echo system
• An incident of ultrasound will be partially
reflected and transmitted at each interface of
the test piece, including the backing.
• It is the pulse partially transmitted at each
interface of the test piece, including the backing.
It is the pulse partially transmitted at the
interface that undergoes more or less total
reflection at this free surface.
• When the bonding at the interface is intact, the
amplitude of the reflected pulse will be fairly low,
in contrast to the amplitude of the transmitted
pulse that travels through the substrate and is
reflected at its free boundary. If a defect is
present at the interface containing air, or
indicating another way that the joint has been
disbanded, the amplitude of the related
ultrasonic pulse will show an increase. This
increase is due to the very low acoustic
impedance at the site.

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 Thermographic detection of debonding areas
• Heat flux passing through a coated
substrate will provide a uniform
temperature on the surface,
providing there is no flaw or
debonded area of the coating.
When a flaw or debonded site is
present, the flow of heat flux is
interrupted and a decrease in
temperature is detected on the
surface.
• The actual shape of the area where
the temperature decreases is made
visible at the surface by in infrared
sensor. This can be seen in Figure
• The primary advantage of thermographic detection methods is the fact that they yield remote
mapping of the distribution of temperature on a surface, whatever the cause may have been.
• This principle has been applied successfully to the detection of subsurface flaws, which may occur as
a consequence of any deterioration in the bonding quality of coating and substrate.
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 Application of acoustic emission analysis for
monitoring the outset of coating detachement
• Using very sensitive acoustical sensors, by
specific burst of (misty ultrasonic) pulses,
this principle has also been proposed for
monitoring the behavior of adhesive joints
under load.
• The acoustic signals obtained are related to
individual fracture events in the test system.
• Normally, it will be the detachment of the
film that is indicated in this way. It is also
possible that any separation within the film
(e.g., between binder matrix and pigment)
could also cause acoustic signals, but in all
probability on a lower level of intensity.
• This procedure appears to provide a
potentially promising method of detecting
flaws in a coating system. However, a great
deal of information is required if the
preliminary results are to be interpreted
correctly.

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