he November 1996 column

dealt with the damaging ef-

fects of compressive and ten-
sile stresses resulting from the ex-
pansion and contraction of paint
films as they respond to changes in
humidity. This month, we will con-
sider in more detail the effect of
small molecules as penetrants into
the dry film. While the films re-
sponse to such penetration parallels
its response to humidity, the magni-
tude of the response may be signifi-
cantly greater, and the consequences
may be more catastrophic.
This article will review the action
of penetrants through films, the in-
fluence of free volume and glass
transition temperature (T
g
), penetra-
tion-related primer failures, and the
measurement of solvent resistance
of coatings.
Free Volume and Penetrant
The January 1996 column intro-
duced the concept of free volume.
In discussing the volumetric expan-
sion of a film caused by the entry
and accumulation of penetrants into
the film, we revisit free volume.
It is largely through free volume
holes that small penetrants enter in-
tact films, working their way down-
wards into the film through adjacent
free volume sites in successively
deeper molecular layers. These sites
or holes become available as the
polymeric structure of the film vi-
brates with the kinetic energy of the
molecule. (These vibrations are of a
very high order, 10
12
times each
second.) As the molecule or pene-
trant moves from one molecular
ingress and the accumulation of
even more penetrant.
In the case of thermoplastic sys-
tems, active solvent penetrants pro-
gressively dissolve the film. In cross-
linked systems and in thermoplastics
where the penetrant is not an active
solvent, the extent of penetrant accu-
mulation and therefore swelling will
depend on the solubility of the pen-
etrant in the coating and the rate of
its diffusion within the film. These
are affected by the molecular struc-
ture of the polymer and penetrant,
the size and shape of the penetrant,
the affinity of the penetrant for
groups within the polymer, the
cross-link density of the film, and the
relationship T-T
g
. In less amorphous
thermoplastics, film structure is very
important, as is the molecular weight
of the polymer, the preponderance
of crystalline areas, the degree of
secondary valency bonding between
chains, and again T-T
g
. These factors
will largely dictate the rate of entry
and diffusion of the penetrant.
layer to the next deeper layer, the
vacant site in the original layer is
taken up by a new molecule of pen-
etrant that enters the film at the lo-
cation being vacated.
The insertion of a highly polar
molecule, like water, into the poly-
meric continuum may provide a site
to which other water molecules are
attracted. This site will feature a hy-
drogen-bonded accumulation of
water molecules.
In other cases, functional groups
on the polymer structure of the
binder will facilitate the ingress and
accumulation of penetrants, for ex-
ample, hydroxyl groups on epoxies
and amide groups on urethanes. The
accumulation of penetrant molecules
at such hospitable sites within the
polymeric matrix may eventually pry
apart the chains of the polymer. The
penetrants overcome some of the
secondary associations that, espe-
cially in thermoplastics, hold the film
together and thus reduce the T
g
of
the film by plasticization. The weak-
ening of the film allows increased
MAY 1997 / 69
T
continued
TROUBLE with PAINT
Effects of Solvents on
Coating Films
Fig. 1 - Solvent attack
on a cross-linked
epoxy film
Figures courtesy
of the author
by Clive H. Hare,
Coating System Design Inc.
Copyright 1997, Technology Publishing Company
Copyright 1997, Technology Publishing Company
When the take-up of penetrant
is sufficient to induce severe changes
in non-soluble films, severe compres-
sive stresses build up within the
solvated film and cause mechanical
failure. Initially, this failure is centered
at the interface of the film and its
substrate and is first manifested as
blistering from localized de-adhesion.
In some cases, the stress-induced de-
adhesion may be facilitated by an
accumulation of penetrant at this in-
terface, which displaces the coating
film. With the more aggressive sol-
vents, this effect is often secondary
to film distention, which precedes
any interfacial accumulation. In the
more severe cases, the solvated film
may expand so much that it delami-
nates entirely, wrinkling into furrows
(Fig. 1). Delamination may be accom-
panied by concomitant vertical cohe-
sive failure, cracking, or breaking of
the film, as the film is strained be-
yond its elongation at break. (The
mechanical properties of the film, in-
cluding modulus, yield values, tensile
strength, and elongation properties,
constantly change during solvent at-
tack. The film becomes softer and
weaker, if more flexible, than before
solvent impact.) This type of failure is
typical of the action of paint re-
movers. (See pp. 73-74.)
T
g
and Penetrant Action
Because free volume availability and
molecular mobility within the coat-
ing film are greatly reduced at tem-
peratures below the T
g
of the film, it
follows that penetration is signifi-
cantly reduced as T-T
g
becomes
negative. There is some free volume
(about 2.5 percent of the volume of
the film) below the T
g
. Some re-
searchers
1,2
have concluded that
minimization of diffusion is found at
some secondary threshold below the
T
g
, T

, at which there is no configu-

rational entropy.
If impermeability to solvent is the
paramount design criterion, the
binder selection should ensure that
film T
g
is above the service tempera-
ture (i.e., T-T
g
is negative). It should
also remain above the service tem-
perature. The plasticization of a film
by the absorption of a penetrant that
depresses the T
g
of the film below
the service temperature may initiate
significantly increased absorption
and system failure. This degree of
plasticization may occur in immer-
sion service, where the temperature
of the liquid is temporarily increased
above the T
g
. Without post curing,
in fact, some researchers such as
Wicks believe that maintaining the
T
g
well above T can be difficult with
films cured at ambient temperature.
Cross-linking of a thermosetting
polymer becomes 2 or 3 times slow-
er as the T
g
rises during cure above
the ambient temperature. Essentially,
air drying thermosets never achieve
T
g
levels much above the tempera-
ture at which the film is formed.
This, Wicks believes, is a factor in
the superior corrosion resistance of a
baked system compared to air dry-
ing offsets.
3
TROUBLE with PAINT
70 / Journal of Protective Coatings & Linings
continued
Fig. 2 - Wrinkling of oil-based primer
recoated with a high performance
thermoplastic coating (lacquer)
Copyright 1997, Technology Publishing Company MAY 1997 / 73
TROUBLE with PAINT
The ingress of penetrants into a
coating film decreases T
g
in both
thermosets and thermoplastics. Not
only does decreased T
g
reduce the
systems resistance to the penetra-
tion of additional molecules of the
same penetrant, but also the in-
creased free volume will facilitate
the penetration of other types of
small molecules. The corrosion resis-
tance of a highly solvated film will
be poorer than one that is free
of solvents.
Residual hydrophilic solvents such
as cellosolve acetate in high-build
vinyls have compromised the perfor-
mance of such systems in water
service, for example. Similarly, the
depression of T
g
from the ingress
of moisture into the film also de-
creases the films resistance to inva-
sion by oxygen.
In extreme cases, high T
g
ther-
mosets of high cross-link density
(e.g., trimerized cyanate esters and
thermosetting polyimides) will take
up little water and solvent and will
change little dimensionally, even
in immersion service. In films of
highly crystalline polymers, such as
those based on the fluoropolymers,
acrylonitrile, or polyolefins, the
polymer will exhibit little take-up
of even the most powerful pene-
trants, and consequent swelling will
again be minor. Systems having
lower cross-link density, such as
epoxy polyamides and those lower
density systems rich in polar groups
(alkyds), will, conversely, exhibit
considerable volumetric expansion
in the presence of water and sol-
vents. Fortunately, certain amine-
cured epoxies, polyesters, and
vinyl esters give adequate imperme-
ability to oxygen, solvents, and,
relatively speaking, to water, after
ambient cure.
Lifting Failure with
Solvent-Sensitive Primers
In recoating one film with another,
the absorption of carrier solvent
from the recoat systems into the al-
ready applied films of the primer,
undercoat, or old coating is to some
degree inevitable, as is the conse-
quent deformation of the existing
film. Solvent absorption may or may
not cause problems. Lacquers and
latex system films may partially or
completely redissolve in the solvent
systems of the newly applied finish,
even allowing some interfacial asso-
ciations between molecules of one
coat and another. These films rarely
give problems. The resultant solvent
weld or disappearing interface be-
tween the 2 layers will normally
guarantee adhesion.
Old, well-cured oxidized systems,
baked systems, and other thermosets
continued
Paint Removers
An extreme example of penetrant
attack on coating films is seen in the
action of paint removers (Fig. a).
Such removers are based on designed
solvent mixtures primarily made up
of small molecules such as methylene
chloride and methanol. These mole-
cules readily insert themselves into
the free volume spaces within the
polymeric matrix. Strong electronega-
tive groups (chlorine, hydroxyls)
allow for good secondary valency
bonding of the solvent with the poly-
mer, which encourages absorption.
Evaporation of the solvent (a process
that opposes absorption) is reduced
by trapping the solvent against the
film using wax additives. The addi-
tives float to the top of the paint re-
mover surface. There, they precipitate
and form a barrier above the solvent.
Excessive free volume expan-
sion, resulting from the absorption of
sensitive substrate. The characteristic
wrinkling or puckering of the film be-
large quantities of solvent by the
coating, produces interfacial failure of
the paint system with a less solvent-
Fig. a - Mechanism of paint remover activity
PAINT REMOVERS continued on page 74
Copyright 1997, Technology Publishing Company
are also rarely affected by solvent at-
tack in recoating. However, their
cross-link density is usually high
enough to resist excessive solvent
absorption and consequent film de-
formation. In fact, it is often more of
a problem to secure good adhesion
to these films because of the ab-
sence of solvent attack. A recoat
window related to the degree of
primer cure is often utilized when
recoating epoxies and urethanes.
Entirely more vulnerable to attack
by a wide range of solvents are ther-
mosetting systems of very low cross-
link density, such as recently ap-
plied oxidizing films (long oil
alkyds). These films are slow to de-
velop appreciable cross-link density
and, therefore, solvent resistance.
Vinylated alkyd copolymers
(styrene and vinyl toluenated
alkyds) are particularly vulnerable in
this respect. Here, a rapid full cure is
sacrificed for fast initial dry.
4
The
films are sensitive to solvent during
a long intermediate cure period be-
tween the initial drying (lacquer
mechanism) and full cure (oxidative
mechanism). The large amounts of
vinylation reduce the available un-
saturation, so that oxidation takes far
longer than with the equivalent oil-
modified alkyds. Other systems
showing fast touch-dry/slow
through-dry properties, such as very
high-solids medium and long oil
alkyds, are also very susceptible to
this type of attack. Here, aromatic
solvents and oxygenated solvents
will rapidly penetrate the still incom-
pletely cured primer, producing se-
vere swelling of the film and, as a
consequence, a wrinkling and lifting
from the subfilm (Fig. 2).
Less attack is likely using finish
coats based on aliphatic hydrocar-
bons such as mineral spirits and
VM&P naphtha. While a slightly more
aggressive solvent than mineral spir-
its, VM&P naphtha evaporates very
rapidly, which diminishes contact
time. Made up of larger, more un-
wieldy branch chain molecules in-
stead of the small, compact structures
that typify the aromatics, these sol-
vents are similarly far less dangerous
to use over sensitive, newly applied
films because they are less easily in-
serted into the polymeric matrix.
Factory-primed with alkyds and oil
paints, structural steel members,
light miscellaneous metal pieces, or
other equipment often exhibit lifting
failure in demanding environments
where surfaces are to be refinished
with epoxies, urethanes, and other
high performance topcoats. During
application of the finish coat or soon
after, the primer wrinkles and lifts
from the metal as if it had been
TROUBLE with PAINT
74 / Journal of Protective Coatings & Linings
trays the large increase in surface
area (as compared to the area of the
substrate) that accompanies the volu-
metric increase of the film. The film
may remain locally adherent at dis-
crete points where stress has been
dissipated locally by the loss of adhe-
sion of the film in adjacent areas. Lo-
calized adhesion leads to locally un-
restricted film distortion and reduced
stress on the remaining adjacent ad-
hesive anchorages. However, lateral
propagation of adhesion loss at the
remaining anchorages usually results
in eventual total delamination. In this
case, the film puckers up.
Solvents used in paint removers
are readily imbibed into even highly
cross-linked films, such as epoxies
and polyurethanes, as well as into
aged oxidizing films. These solvents
will dissolve lacquers and latex.
Methylene chloride is, of course,
the target of regulation. (Toxicity con-
These groups may attack vulnerable
sites on the polymer, causing hydrol-
ysis and thereby further facilitating
solvent ingress and deformation of
the film. This type of remover is
rarely necessary with alkyds or even
polyamide-cured epoxies. Carboxylic
acids may, however, be valuable in
removing more highly cross-linked
epoxies. Paint removers based on so-
lutions of sodium and potassium hy-
droxide in gelled solvents may be
used to remove urethanes and oil
systems. Small amounts of water and
surfactants may be introduced to fa-
cilitate alkaline hydrolysis of the ester
or amide groups within the film. The
same principle without the solvent is
used in poultice-type removers popu-
lar for the field removal of lead-based
paint systems. These highly alkaline
materials are trapped against the film
with water-impermeable paper or
plastic sheet, and the hydrolysis of
the polymer proceeds over a more
extended period of time.
cerns have always limited the use of
methanol in these compositions to
about 4 percent.) Finding non-toxic re-
placement solvents of equal effective-
ness poses some difficulty. Methylene
chloride and methanol are small,
streamlined, highly polar materials that
are low in molecular weight and effec-
tively penetrate and expand the free
volume of even the most cross-linked
systems. Some small, compact mole-
cules, such as the cyclic lactam, n-
methyl-2-pyrrolidone, have similar
properties but are slower to evaporate
than methylene chloride and
methanol. Delamination, therefore,
may take much longer than is the case
with conventional removers.
Other small, active molecules
have also been used in paint re-
movers. These include the lower car-
boxylic acids (formic acid and acetic
acid) as well as substituted aromatics
such as phenol and cresylic acid.
These materials also have benefits be-
cause of their functional groups.
continued
PAINT REMOVERS
continued from page 73
Copyright 1997, Technology Publishing Company MAY 1997 / 77
TROUBLE with PAINT
treated with paint remover. In some
systems (e.g., the vinylated alkyds
noted above), there is a viable recoat
window both before and after the pe-
riod of solvent sensitivity wherein
these systems may be recoated safely.
Shortly after application, the lacquer-
type drying predominates without oxi-
dation, and the film may be recoated
without mishap. In the very long run,
the film may become more fully oxi-
dized, and here again resistance to sol-
vent attack improves enough to allow
good recoatability. In the long interme-
diate period, however, the conse-
quences of recoating with strong sol-
vent topcoats may be lifting of the
primer. Rapid recoating of such insuffi-
ciently oxidized films with chemically
curing systems may actually lock in a
partially uncured state within a primer
of this type. Thereafter, this type of de-
ficient system will be unusually sensi-
tive to lateral cohesive failure under
applied stress.
Still available is a class of universal
lift-resistant primers that dry rapidly
and may be satisfactorily coated
with lacquers and other strong sol-
vent-containing finish coats. They
are generally inhibitive primers for-
mulated from special phenolic and
rosin-modified short to medium oil
alkyds. Similar alkyds are sometimes
externally modified with phenolic
dispersion resins, giving still further
improvements in recoatability.
The use of solvents in a recoat film
to obtain improved adhesion of the
recoat to the primer (or undercoats)
involves much the same considera-
tions as are noted here, although in
the former case, solvent attack is con-
trolled and used productively.
Solubility and Attack of Solvents
Solvency and the judicious applica-
tion of solubility parameters
5,6
are
the keys to predicting solvent sensi-
tivity of amorphous thermoplastics.
These polymers remain soluble in
the classes of solvents that character-
ize the solubility of the dry resin
type. Even high molecular weight
systems, including thermoplastic
powder coatings, organosols, plasti-
sols, and latex paints, will soften, if
not dissolve, in these solvents.
The actual dissolution of ther-
mosetting ambient-cured epoxies,
urethanes, baked amino, and phenyl
formaldehyde cross-linked films is
precluded by the primary bonded
network of the film structure. How-
ever, solvents may penetrate and
swell systems of this type, especially
those of lower cross-link density. In
the latter case, the more open, cross-
linked structure allows the easier in-
sertion of penetrants. Penetration is
also partially dependent upon solu-
bility characteristics, certainly on the
affinity of the penetrant for the
structural make-up of the film. As
continued
Copyright 1997, Technology Publishing Company
noted above, cross-linked systems
rich in alcohol groups, for example,
will be vulnerable to alcohols and
other polar solvents, while non-
polar coatings will be more resistant
to attack from this type of solvent.
Testing for Solvent Sensitivity
Solvent sensitivity in thermosetting
systems is more likely, therefore, to
be an indicator of the extent of cure.
The rub test with an appropriate sol-
vent (usually methyl ethyl ketone, or
MEK) is a standard qualitative test for
the assessment of cure. In this test, an
MEK-soaked cotton, cloth, or felt tip
of an engineered marker is reciprocal-
ly rubbed across the film, and the
number of rubs required for film re-
moval, loss of gloss, or other change
is noted. Systems showing no effect
after 200 double rubs are considered
cured, although this is hardly a
measure of the extent of cross-link-
ing. In addition, the test is not much
good for differentiating between 2 or
more systems that are satisfactorily
cross-linked. In systems where a rea-
sonable degree of cross-linking is ex-
pected and the film is removed in 20
to 50 rubs, the result would indicate
some problem in the cure condition
(cure time and temperature or mixing
ratio). Immediate solubility of the
films supposedly laid down from two-
pack mixes such as urethanes and
epoxies is usually evidence that one
or another of the components is miss-
ing. Solvent rub techniques are often
used in the field as part of the failure
analysis process. The general degree
of cure may be confirmed by infra-
red spectrophotometry.
Solvent immersion testing may be
a better measure of relative solvent
resistance in highly cross-linked sys-
tems using either the watch glass test
or preferably some kind of covered
immersion test. Coatings are com-
pared by their timed response to the
solvent, which progresses from soft-
ening or blistering to dissolution or
delamination. Watch glass tests using
volatile materials can be particularly
frustrating because in spite of the
cover, solvent evaporates rapidly. In
addition, the test requires continual
monitoring with many applications.
The effect of repeated solvent ab-
sorption and desorption is probably
fatiguing to the film but thwarts even
a rough qualitative assessment of the
relative effect of different solvents on
the same film or the response of
multiple films to the same solvent.
A more quantitative assessment of
solvent sensitivity may be obtained by
weighing small coupons of totally
coated metal or glass before, during,
and after solvent immersion, and plot-
ting the weight change data against
time (Fig. 3). In this way, both the
amount of absorbed material and the
rate of absorption may be assessed,
as well as the extent of dissolution (or
solid removal) after the test is termi-
nated. Differences in the weight of
the fully dried films before and after
immersion may show the loss of ex-
tractables. Some error may occur be-
cause of weighing time, but this usu-
ally takes less than 30 seconds with a
modern analytical balance.
Matching the temperature of the
test with the service application is
also important in testing for solvent
sensitivity. Hot solvent is far more de-
structive than cold solvent, and hot
films (above their T
g
) are more sensi-
tive than cold films. Solvent contact at
high temperature may yield quite dif-
ferent results from low temperature
testing on the same film. In applica-
tions where solvent contact is not en-
closed, the mitigating effects of evap-
oration will also be magnified in the
case of hot solvent.
Recoatability
Solvent sensitivity is often used to
advantage in the design of coating
systems, where it may be used to
improve the intercoat adhesion be-
tween successive films.
In such recoating, there are no de-
vices such as the wax used in paint
removers to trap the solvent systems
against the old coating and retard
their evaporation long enough so
that they may attack the existing
film. Under most circumstances, the
solvent system will evaporate from
the finish before it can absorb ap-
preciably into the paint film and
produce the free volume expansion
necessary to good intercoat adhesion,
or, in extreme cases, compressive
stresses sufficient to induce failure.
TROUBLE with PAINT
78 / Journal of Protective Coatings & Linings
continued
Fig. 3 - Solvent resistanceweight change over time, before, during, and after immersion
Copyright 1997, Technology Publishing Company
MAY 1997 / 81
TROUBLE with PAINT
Contact time between solvent and the
exposed film will be increased with
high film thickness recoats or where
barrier-type pigmentations (aluminum
flake) are used in the recoat. In some
cases, such excessive contact time
may be long enough to cause solvent
attack on the primer, particularly
where high boiling (slow evaporat-
ing) solvents are used. Low molecular
weight solvents (small molecules)
such as acetone and toluene, which
are more aggressive than larger mole-
cules and which might easily pene-
trate the film, usually evaporate too
fast to do so. Conversely, larger mole-
cules such as methyl isoamyl ketone,
diisobutyl ketone, and high flash
naphtha may stay in contact with the
existing film long enough to facilitate
entry, but they are often too large to
readily penetrate the existing film.
Compact solvents with cyclic struc-
tures, such as cyclohexanone and n-
methyl-2-pyrrolidone, are small
enough to enter the film easily but
are relatively slow to evaporate.
These solvents may be more aggres-
sive in solvating the surface of the
existing film. They have been used
to soften hard, well cured thermosets
before coating. In lacquer-based sys-
tems made up of amorphous ther-
moplastic-based coatings, the poten-
tial dissolution of a lower coat by the
solvents of a subsequently applied
coat ensure a good bond with sol-
vent and solubilized binder intermin-
gling across the interface.
The swelling of thermosetting
primers by solvents in the finish may
also be used, especially where the
state of cure of the primer film remains
incomplete. As cure advances with
time (as T
g
increases), the technique
becomes progressively more difficult
to apply. This fact is indicated in the
recoat window of the system pub-
lished by coating manufacturers. In
many of the better product informa-
tion sheets, this recoat window is ex-
pressed in terms of cure temperatures
involved. Recoat times become pro-
gressively shorter as cure temperatures
increase. It is, of course, possible that
in recoating primers with T
g
values in
the 80 to 90 F (27 to 32 C) range, ap-
plications at 90 to 100 F (32 to 38 C)
may actually facilitate recoating be-
cause of T-T
g
effects.
Shrewd use of solvents in the re-
coat paint may also improve the re-
coatability of well aged gloss films.
Conclusion
Next month, we will review aesthet-
ic difficulties associated with solvent
sensitivity in coating films. JPCL
References
1. G. Adams and J.H. Gibbs, Journal
of Chem. Phys. (Vol. 43, Number
139, 1965).
2. E.N. Dalal, On the Relationship
between T
g
and T, Journal of
Polymer Science, Polymer Letters
Edition (Vol. 22, Number 547,
1984), 547-548.
3. Z.N. Wicks, Free Volume and
the Coatings Formulator, Jour-
nal of Coatings Technology (De-
cember 1986), 23.
4. H.R. Hamburg and W.H. Mor-
gans, Hess Paint Film Defects,
3rd Edition (London: Chapman
& Hall, 1979), p. 284.
5. C.H. Hare, Protective Coatings
Fundamentals of Chemistry and
Composition (Pittsburgh, PA:
Technol ogy Publ ishing Co.,
1994), p. 141.
6. H. Burrell, Solubility Parameters
for Film Formers, Official Digest
(now the Journal of Coatings
Technology) (Vol. 27, Number
369, 1955), 726.
Back issues containing the earlier
segments of the Trouble with
Paint series are available from
JPCL at 800/837-8303.