TROUBLE with PAINT

Adhesive and Cohesive Failure:

Definitions and Fundamental
Macro-Effects
by Clive H. Hare, Coating System Design, Inc.

I
deally, the aging paint film
should erode slowly and steadily
in a more or less predictable
fashion. Any other degradation
may reasonably be classified as a
paint failure, although tradition
would condition us to accept the
cracking and checking of aged oil
paint films and the flaking of clear
polyurethane varnishes over exterior
wood as inevitable and normal. The
failures here, of course, are not so
much material failures (the materials
respond to the exposure in a typical
fashion), as they are a failure in ap-
plication or specification design. Fig. 1
There are certainly coatings that will
Figs. 2a and 2b
give satisfactory, long-term service
(left and bottom)–
as house paints without cracking, Internal stress, produced
and exterior clears on wood may be by shrinkage of an epoxy
formulated to perform under ex- film on solvent loss and
treme conditions without flaking. In crosslinking, sets up strains
within the applied composite
these cases, the appropriate materi-
that are strong enough to
als were simply overlooked when produce substantial
the coating systems were selected. deformation in a thin
It will be our position throughout aluminum substrate.
this series that paint film deteriora- a - The newly “dried” film is
tion involving any kind of delamina- initially flaccid and relaxed.
tion, lateral splitting, cracking, b - After full solvent release
checking, bubbling, or blistering and crosslinking, the film is
should be considered a failure. strong and hard. Internal
strains, which are incurred
Where one may argue that no coat-
as the film polymerizes and
ing will indefinitely tolerate service shrinks, are dissipated by
in some environments without some curling the weak substrate.
manifestations of distress, then a Photos and figures courtesy of
reasonable retort might be that the Clive Hare
use of alternative materials (corro-
sion-resistant alloys, highly crys-
talline plastics, or perhaps glass)
would have been a more appropri-
ate engineering response than the
use of coatings.
continued

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OCTOBER 1995 / 177
 TROUBLE with PAINT

Table 1
Bonding Forces and Binding Energies

Binding Energy
Force Type Description Example (kcal/mole)

Ionic Primary Valency Bonding formed by transfer of valency Metal Salts 150-250
electrons from the outer shell of an
electron-donating atom (metal) into outer
shell of an electron-accepting atom,
to produce a stable valency configuration
in both.

Covalent Primary Valency Bonding formed when one or more Most 15-170
pairs of valency electrons are shared Organic
between 2 atoms. Molecules

Co-ordinate Primary Valency Covalent type bond where both Quaternary 100-200
of shared pair are derived from Ammonium
one of the 2 atoms. Compounds

Metallic Primary Valency Bonding in bulk phase of metals between Bulk Metals 27-83
positively charged metallic ions and the
electron cloud in the lattice points of
the structure.

Hydrogen Bonding Secondary Forces set up between the unshared Water <12
electrons on a highly electronegative
atom on 1 molecule and the weak positive
charge from the “exposed” proton of a
hydrogen atom. (The hydrogen atom is
covalently bonded to an electronegative
atom on a second molecule.)

Dispersion Secondary Weak forces in all molecules that are Most <10
(London) associated with temporary fluctuations Molecules
in electron density caused by the
rotation of electrons around atomic nuclei.

Dipole Secondary Intermolecular forces set up between Polar <5

(Keesom) weak and electronegative charge on Organics
one polar molecule and electropositive
charge on a second polar molecule

Induction Secondary Very weak dipole-like forces between Non-Polar <0.5

(Debye) non-polar molecules set up by weak Organics
dipoles induced by the proximity of
other strongly polar molecules.

If paint is to be considered a vi-
able engineering material, as was
conceived by Mattiello 1 and
Bobalek2, then formulators, speci-
fiers, and applicators must seek to
provide a product that is as durable
as the article it protects, whether
that article is an automobile, a piece
of furniture, or a storage tank. We
cannot, of course, prevent some de-
terioration over time. We can, and
must, however, avoid less natural
breakdown. Certainly the adhesive
and cohesive paint film degradation,
which will be our focus this month,
should never be considered any-
thing but a failure.
Forces that Maintain the
Applied System
Coated metal (and the coated sub-
strate in general) may be considered
a mechanical model. The coating is
1 component, and the metal (or sub-
strate) is a second component. The
boundary between the 2 compo-
nents is known as the interface.
Where more than a single coat of
paint makes up the model, there will
be additional interfaces between the
individual coats. A typical paint sys-
tem made up of 3 coats on a sub-
strate (i.e., the four-component
model depicted in Fig. 1a) will have
3 interfaces: 1 between the substrate
and the lower or primer coat, 1 be-
tween the primer and intermediate,
and 1 between the intermediate and
continued

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OCTOBER 1995 / 179
TROUBLE with PAINT
the finish. It will be our custom
throughout this series to refer to the
whole (the substrate, primer mid-
coats, and finish) as the paint system
composite, or paint system. There is
also an interface between the finish
coat and the environment, but this
interface is not relevant to our dis-
cussions at this time.
In such a model, adhesive forces
operate across the interface to hold
the film to the substrate or any 2
films together. Adhesive forces are
set up as the paint is applied to the
substrate (or lower film), wets it,
and dries. The magnitude of these
forces will depend on the nature of
the surface and the binder of the
coating (the glue that holds the coat-
ing together). Adhesive bonding
forces may be broadly categorized
as 1 of 2 types, primary valency
forces and secondary valency forces.
The primary bonding forces are a re-
sult of chemical bonds between re-
180 / Journal of Protective Coatings & Linings
active functional groups on the mol-
ecules of the binder with comple-
mentary reactive groups on the sub-
strate. These very strong bonding
forces give much higher adhesion
values than do secondary forces
(Table 1).
Secondary valency bonding is
based on much weaker physical
forces typified by hydrogen bonds
and Van der Waals forces. The latter
result from weak electrical differ-
ences between non-reacting sites on
the paint binder and substrate.
These forces are more likely to be
found in materials (binders and sub-
strates) having hydroxyls and other
polar groups than on non-polar sur-
faces such as polyethylene. Sec-
ondary valency forces are the same
forces that make it difficult to sepa-
rate the mating surfaces of 2 pieces
of flat glass or 2 transparencies.
Cohesive forces hold the paint
film itself together. That is, they
maintain the integrity of the film
continuum, which is the continuous
strata of the in-place film. The foun-
dation of these forces is primarily
the polymeric skeleton of the binder
itself, which also holds the pigment
in place, and, as noted in the pre-
ceding paragraphs, holds the film to
the substrate at the interface. For the
most part, this polymeric skeleton is
made up of primary valency-bond-
ed, high molecular weight polymeric
chains. In some films (lacquers, latex
paints), however, some degree of
secondary bonding allows individual
chains to associate. In networked
(crosslinked) polymers, these inter-
chain associations are replaced with
primary bonds to give a wholly pri-
mary bonded skeleton.
The metal substrate itself is also
maintained by cohesive forces. In
metal, cohesive forces result exclu-
sively from primary bonds (metallic
bonds). In concrete, much of the co-
Copyright ©1995, Technology Publishing Company

hesive bonding is ionic in nature,
while in wood and plastics, the pri-
mary valency bonding is covalent. In
thermoplastic substrates, some old
coating substrates, and other organ-
ics (leather, paper, etc.), secondary
valency bonding may also play a
part in substrate cohesion. Cohesive
forces in the substrate are normally
(though not universally) much
greater than the cohesive forces
holding the paint film together.
Straining Forces in the
Coating Film
Opposing the adhesive and cohesive
forces that maintain the integrity of
the model are strains within the
model induced by internal and ex-
ternal stresses applied to it. For the
purposes of these discussions, a
strain may be defined as a deforma-
tion incurred within the film as a re-
sult of the imposition of a force (or
stress) upon it.
As illustrated in Fig. 1b, there are
2 principal kinds of stress applied to
coating films, internal stress and ex-
ternal stress. As solvent or water
leaves the film and as the film solidi-
fies or dries from the applied liquid
paint, the film shrinks slightly. The
Fig. 3
Copyright ©1995, Technology Publishing Company
TROUBLE with PAINT
internal stresses produced by the
film’s resistance to such shrinkage
set up strains within the film and at
its interface with the metal or lower
film.
The role of internal stress in paint
film failure should not be mini-
mized. As demonstrated in Figs. 2a
and 2b, even in epoxy systems,
where shrinkage stresses are not
large, they are sufficient to greatly
distort a weak substrate such as alu-
minum foil. On substrates that are
stronger than aluminum foil, e.g.,
structural steel, dissipation of the
strain is, of course, not possible by
deformation of the substrate, and
the strain is stored within the curing
film. With such a film, the resulting
film (represented by a mechanical
model) is less capable of accommo-
dating additional strains created as
the model responds to external
stresses from the environment.
The sources of external stresses
range from physical abuses such as
impacts and abrasions (e.g., defor-
mations occurring as the painted
metal is bent or stamped) to recur-
ring cyclic deformations (e.g., vibra-
tion of the metal). A universal type
continued
OCTOBER 1995 / 181
 TROUBLE with PAINT

of external stress is cyclic hygrother-

mal stresses, which affect all paint
films daily. These stresses are caused
by the differential response of paint
film and metal (or other substrate)
to temperature and humidity. Both
components respond to temperature
by expanding under hot conditions
and contracting under cold condi-
tions but to different extents.
This cycling dimensional change
gradually fatigues even an unsup-
ported film.
The differential response of an ad-
herent film and substrate will severe-
ly stress the adhesive and cohesive
integrity of the system. Additionally,
the water absorption of the film
under conditions of high humidity
(or, worse still, immersion) and the
subsequent desorption of water
under dry conditions will produce
similar dimensional distortions.
These conditions create shear and
tensile stresses (Fig. 3) within the
coating system and at the interface,
if not in the substrate. Such humidi-
ty-induced gradients may well be of
equal or greater significance com-
pared to the thermal gradients.
Humidity gradients are particularly
stressful on substrates such as wood,
where absorbed/desorbed water will
also produce considerable substrate
distortion. This may lead to in-
creased shear and tensile stresses as
the paint film and substrate respond
to the humidity gradients to different
extents and at different rates.

Adhesive and Cohesive

Paint Failure
Adhesive failure (peeling, flaking,
delamination, and other manifesta-
tions shown in Figs. 4a and 4b) oc-
curs where, in the presence of op-
posing stresses, the adhesive forces
are insufficient to hold the paint to
the substrate (whether that be a
metal, wood, concrete surface, or a
lower coat of paint).
Cohesive failure occurs where the
continued

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 TROUBLE with PAINT
cohesive forces are insufficient to
maintain the integrity of any individ-
ual film (or substrate) in the pres-
ence of the same opposing stresses.
Cohesive failure may involve a verti-
cal splitting or rupture (cracking,
checking, alligatoring, crows footing,
etc., which is shown in Fig. 4c) or a
horizontal rupture (lateral splitting
depicted in Fig. 4d).
Stresses applied
to any element
of an intact
coating system
will be
transferred
throughout the
entire system.
Cracking is more likely to occur in
cohesively weak finish coats. These
are supported below but have no
upper support. Lateral splitting is
more likely in cohesively inadequate
undercoats and primer films that are
supported both above and below by
(sandwiched between) more cohe-
sively substantial layers (the sub-
strate and the finish). Mudcracking
in zinc-rich primers (and other
weak, low binder content paint hav-
ing pigment volume concentration/
critical pigment volume ratios in ex-
cess of unity) is an example of a
vertical cohesive failure. This type of
failure occurs before recoating as
the zinc-rich primer dries. At this
time, the primer may be temporarily
considered a finish.
Stresses applied to any element of
an intact coating system will be
transferred throughout the entire
system. As a result, the coating may
fail at a site weaker than the one
184 / Journal of Protective Coatings & Linings
where the stress is directly applied.
Thus, a stone striking a flexible fin-
ish coat may produce a failure in a
lower, less flexible primer (Fig. 5).
Similarly, a coating with high in-
ternal stress applied over an aged
existing coating system made up of
weakened interfaces may not pro-
duce failure in the immediate paint
film to which it is applied, but may
produce failure at some other site
within the total coating system. Gen-
erally, when an intact coating system
is stressed to failure, failure will
occur at the weakest site within the
system, either adhesively across
some weak interface, or cohesively
within some insufficiently continu-
ous film. In practice, this may be at
an interface below the site of the
new application. It is often at the
substrate of the original (now aged)
primer and the original substrate.
The problem is a major concern for
the practice of overcoating for the
maintenance of bridges and other
structures coated with lead-based
paint (Fig. 6).
These, then, are the macroscopic
manifestations of adhesive and co-
hesive failure. Specific examples of
such failure may all be reduced to
these appreciations. To fully under-
stand the mechanics of such failure
so we may eventually manipulate
the system to avoid the problem, we
must understand the involved phe-
nomena on a molecular level.
Measuring of Stress and Strain
The entire topic of stress and strain
response in paint systems has been
long neglected. Thanks to the efforts
of pioneers like Hill, Ikeda, Zosel,
Croll, and Touissant, we have over
the past 20 years begun to apply
and adapt approaches long em-
ployed in plastic, fiber, and rubber
and elastomer technologies, to un-
derstand and quantify the phenome-
na involved.3-8
In coatings, the work is seriously
complicated because a coating film
Copyright ©1995, Technology Publishing Company

Fig. 4
Fig. 5
is by definition substrate-supported,
while other technologies deal with
unsupported polymers.
The cross section of coating films,
which is minimal compared to
plastics or composites, gives practi-
cal problems in sample preparation.
The necessity of removing solvent
or water from the drying film is
also critical to adapting many of
the measurement techniques to
coatings.
Notwithstanding these difficulties,
we can now mathematically define a
required mechanical profile (the
Copyright ©1995, Technology Publishing Company
TROUBLE with PAINT
manner in which a paint film should
respond to an applied stress) for a
given application. This also permits
correlation of molecular structure
with that profile. Progress is tenta-
tive. We still cannot quantify the
stress and strain patterns distributed
throughout a multi-layered existing
composite. Such quantification might
one day be used to predict the re-
sponse of that system to stress in
service. We are, however, beginning
to identify directions of such ap-
proaches, and this alone may help
continued
OCTOBER 1995 / 185
 TROUBLE with PAINT

Fig. 6 - Adhesive failure of a newly overcoated lead paint composite from an original mil
scale substrate. Failure is related to high internal strain within the composite produced by
shrinkage of the newly applied epoxy. This has diminished the ability of the composite to
accomodate external stresses (probably hygrothermally derived) that are applied to the
coating system in service.
Photo courtesy of Lloyd Smith, Corrosion Control Consultants & Labs Inc.

to reduce some misapplications in 3. L.W. Hill, Mechanical Properties

the field.
Conclusion
In the next several months, we will
review the concepts of paint film
physics that directly affect our un-
derstanding of the mechanical prop-
erties of coating films. As part of
this, we will address other aspects of
our science, such as solvent loss and
film formation, the diffusion of pen-
etrants into and out of a film, and
the effect of cure temperature on
performance.
In our next segment, we will re-
view the molecular structure of coat-
ing film binders on which cohesion
and adhesion so much depend. JPCL
References
1. J.J. Mattiello, “Protective Organic
Coatings as Engineering Materi-
als,” Proceedings of the Ameri-
can Society for Testing Materials,
46, June 26, 1946, (Philadelphia,
PA) ASTM, 1946.
2. E.G. Bobalek, “Paint Among En-
gineering Materials” Official Di-
gest (December 1962), 1,295.
Copyright ©1995, Technology Publishing Company
of Coatings, Federation Series on
Coatings Technology, (Blue Bell,
PA: Federation of Societies for
Coating Technology, 1987).
4. L.W. Hill, “Stress Analysis—A
Tool For Understanding Coatings
Performance” Progress in Organ-
ic Coatings, 5 (1977), 277.
5. S.G. Croll, “Adhesion Loss Due
to Internal Stress” JCT (June
1980), 35.
6. S. Ikeda, “Dynamic Viscoelastici-
ty of Coating Film” Progress in
Organic Coatings, 1 (1973), 205.
7. A. Toussaint, “Influence of Pig-
mentation and the Mechanical
Properties of Paint Films”
Progress in Organic Coatings, 2,
(3), (June 1974), 237.
8. A. Zosel, “The Mechanical Be-
haviour of Coating Films”
Progress in Organic Coatings, 8,
(1), (1980), 47.
9. M.B. Roller and J.K. Gillham,
“Application of Dynamic Me-
chanical Testing to Thermoset
and Coatings Research and De-
velopment,” JCT (January 1978),
57.
OCTOBER 1995 / 187