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How Moisture Affects Adhesives, Sealants, and Coatings

Article  in  Metal Finishing · October 2011

DOI: 10.1016/S0026-0576(13)70070-9

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adhesion&bonding
How Moisture Affects Adhesives,
Sealants, and Coatings
M oisture is the substance that
causes the greatest difficulties
in terms of environmental stability
for many adhesives, sealants and
coatings (ASCs). Water can be an
exceptional problem because it is
very polar and permeates most poly-
mers. Other common fluids, such as
lubricants and fuels, are of low or
zero polarity and are not as likely to
significantly permeate and weaken
these materials.
Moisture can degrade ASCs in
three distinctive ways.
• Moisture can degrade the
properties of the bulk polymer
itself.
• Moisture can degrade the adhesion
properties at the interface.
• Moisture can also degrade the
properties and cause dimensional
changes of certain adherends.
This article will focus on the affects
and attack mechanisms of moisture
on polymeric adhesives, sealants, and
coatings.
Affect on the bulk polymer. Moisture
can alter the properties of the bulk
material by changing its glass transi-
tion temperature (a measure of the
molecular strength) or by chemically
reacting with the polymer—a process
called hydrolysis. But before these
mechanisms occur, the moisture
must first find its way into the bulk
polymer.
Internal degradation within the
bulk ASC occurs primarily by
absorption of water molecules into
the polymer structure. All polymers
will absorb water to some extent.
Moisture can also enter by wicking
xx I metalfinishing I October 2011
than most other polymers. As a
result, these materials are often used
in ASC formulations where resist-
ance to moisture is essential.
Water permeation in polymers gen-
along the adhesive-adherend inter-
face or by wicking along the inter-
faces caused by reinforcing fibers and
erally lowers the glass transition tem-
perature of the polymer by reducing
the attractive forces between mole-
the resin. Deterioration occurs more cules. This causes swelling and gener-
quickly in a 100% RH environment al plasticization of the polymer. The
than in liquid water because of more effect of absorbed water on the
rapid permeation of the vapor. mechanical properties of room tem-
The water ingress properties of var- perature-cured epoxy adhesives is
ious polymers can be assessed by val- shown in Table 2. Water lowers ten-
ues of their permeability coefficient sile strength and modulus but
and the diffusion constant of water increases elongation at break. These
(Table 1). The permeability coeffi- properties generally recover fully
cient is defined as the amount of when the polymer is dried, unless
vapor at standard conditions perme- irreversible hydrolysis (see below) has
ating a sample that is 1 cm sq. and 1 taken place.
cm thickness within 1 sec with a Some polymeric materials, notably
pressure difference of 1 cm Hg across ester-based polyurethanes and cer-
the polymer. The diffusion coeffi- tain epoxies, will chemically change
cient is a measure of the ease at or “revert” when exposed to humid
which a water molecule can travel conditions for a prolonged period.
within a polymer. Reversion or hydrolysis causes the
Both epoxies and phenolics show adhesive or sealant to break down by
relatively low diffusion rates and are losing molecule weight. This results
less susceptible to moisture attack in reduced hardness, strength, and,
Polymer Temperature, °C P x 10-9 D x 10-9
Vinylidene chloride 25 1.66 0.32
/acrylonitrile
copolymer
Polyisobutylene 30 7-22 NA
Phenolic 25 166 0.2-10
Epoxy 25 10-40 2-8
Polyvinyl chloride 30 15 16
Polymethyl 50 250 130
methacrylate
Polyethylene (low 25 9 230
density)
Polystyrene 25 97 NA
Polyvinyl acetate 40 600 150
Table 1. Permeability Coefficients (P) and Diffusion Constants (D) of Water into Various
Polymers.1
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adhesion&bonding
Exposure Conditions Weight gain, % Tensile Elongation Modulus, MPa Failure Mode
strength, MPa at Break, %
Epoxy A
None 0 73 5 1880 Brittle
3 months at 65% RH 2.9 52 263 623 Ductile
5 days in water at 50°C 9.4 19 260 3.0 Rubbery
5 days in water at 50°C, 3.3 76 5.7 1980 Brittle
then dry at 60°C for
2 days
Epoxy B
None 41 7.1 1700 Ductile
24 hours in water at 24 37 1020 Ductile
100°C
24 hours in water at 53 6.8 1560 Ductile
100°C, then dry at 65°C
for 2 days
Table 2. Effect of Water on Mechanical Properties of Epoxy Structural Adhesives.2

it more easily. before this occurs the sealant usual-

Figure 1. Hydrolytic stability of potting compounds.
Materials showing rapid loss of hardness in this test soften
similarly after 2-4 years in high temperature, high humidity
climate zones.3
in the worst cases, transformation
back to a fluid.
The rate of reversion, or hydrolyt-
ic instability, depends on the chem-
ical structure of the base polymer,
its degree of crosslinking, and the
permeability of the adhesive or
sealant. Certain chemical linkages
are prone to hydrolysis. Reversion
is usually much faster in flexible
materials because water permeates
Figure 1 illustrates the
hydrolytic stability of vari-
ous polymeric materials
determined by a hardness
measurement after expo-
sure to high relative humid-
ity aging. A time period of
30 days in the 100°C, 95%
RH test environment corre-
sponds approximately to a
period from 2 to 4 years in a
hot, humid climate.
In the case of convention-
al construction sealants,
polysulfides, polyurethanes,
epoxies, and acrylics have all
shown various degrees of
sensitivity to moisture.
Hydrolysis causes the break-
ing of bonds within
sealant. Thus, the bond
strength decreases and
cohesive failure results. However,
Figure 2 . Water molecules can penetrate a polymer and then preferentially displace it at the
interface.
ly swells and may cause deformation
or bond failure before hydrolysis can
completely take action.
Affect on the interface. Water can also
permeate the adhesive or sealant
and preferentially migrate to the
interfacial region, displacing the
bulk adhesive material at the inter-
face. This mechanism is illustrated
in Figure 2. It is the most common
cause of ASC degradation in moist
environments.
Strength falls most rapidly at the
beginning of the aging process and
then slows down to a low or zero rate
of degradation. The mode of failure
in the initial stages of aging usually
is truly cohesive (i.e., failure within
the the material itself). After five to
seven days, the failure becomes one
of adhesion. It is expected that water
vapor permeates the adhesive

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adhesion&bonding
through its exposed edges.
The water molecules are then
absorbed into the adhesive and pref-
erentially concentrate on the metal
adherend, thereby, displacing the
adhesive at the interface. This effect
is greatly dependent on the type of
adhesive and the adherend material.
2. Comyn, J., Adhesion Science,
Chapter 10, Royal Society of
Chemistry, Cambridge, 1977.
3. Bolger, J. C., “New One Part
Epoxies are Flexible and
Reversion Resistant”, Insulation,
October 1969.

Affect of the bulk substrate. Certain

substrates, notably wood but also
other materials such as laminates
and certain plastics, will change
dimensions significantly when
exposed to variations in ambient rel-
ative humidity or moisture. Many of
these materials are also anisotropic,
so dimensional change will be
greater in one direction than in
another. Such change can result in
large internal stress at the interface
and even warpage. The adhesive,
sealant, or coating must be selected
with sufficient elongation to with-
stand these dimensional changes.
Another way moisture can degrade
the strength is through hydration or
corrosion of the metal oxide layer at
the interface. Common metal oxides,
such as aluminum and iron oxides,
undergo hydration. The resulting
metal hydrates become gelatinous,
and they act as a weak boundary
layer because they exhibit very inade-
quate bonding to their base metals.
Thus, the ASC used for these materi-
als must be compatible with the
firmly bound layer of water attached
to the surface of the metal oxide
layer.

BIO
Edward M. Petrie is the sole proprietor of
EMP Solutions, a Cary, N.C.–based con-
sulting firm focused on solving problems
in the adhesives and sealants industry. He
also works as a technical expert for
SpecialChem. For more details, please
visit www.specialchem4adhesives.com.

REFERENCES
1. Sung, N. H., “Moisture Effect on
Adhesive Joints”, Adhesives and
Sealants, vol. 3, Engineered
Materials Handbook, ASM
International, 1990.

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