adhesion bonding

Resistance of Adhesives, Sealants,

and Coatings to Corrosive become quite specialized to meet
extreme requirements. As a result,
Environments understanding and planning for
chemical resistance are difficult
processes.

f or an adhesive, sealant, or coat-

ing to be useful, it not only must
withstand the mechanical forces
that are acting on it, but it must also
resist the service environment or the
chemical forces that may also be
applied. Thus, one of the most
important characteristics for these
materials is their endurance to cor-
rosive environments such as those
found in the chemical process indus-
try. This article will focus on the
chemical resistance of adhesives, but
the fundamentals that are discussed
relate to sealants, coatings, and
other polymeric materials as well.
Most organic polymeric materials
used to formulate adhesives,
sealants, and coatings tend to be sus-
ceptible to chemicals and solvents,
especially at elevated temperatures.
Physical properties and durability are
influenced by many environmental
elements. These include: high and
low temperatures; moisture or rela-
tive humidity; chemical fluids; and
outdoor weathering. Table 1 summa-
rizes the relative resistance ofvarious
adhesive types to common chemical
operating environments.
In selecting polymeric materials for
their chemical resistance, certain
generalities must be avoided. The
nature and type of chemical environ-
ments, their concentrations and tem-
perature, the joint design, chemical
resistance of the substrates, and
other specific factors must be consid-
ered. As the combination of factors
becomes large, formulations must
PROCESS OF DEGRADATION BY
CHEMICALS
Chemical factors may affect the
strength and permanence of an
adhesive bond in several ways. The
chemical agents may affect the cohe-
sive (tensile strength, elongation,
etc.) properties of the bulk adhesive
or the adherend. Adhesive properties
(shear or peel strength) at the adhe-
sive-adherend interface could be
affected as well. The extent of deteri-
oration suffered by polymeric mate-
rials is affected by its chemical com-
position and structure, the composi-
tion of the acting medium, and the
conditions of the action. In general,
the degradation process can be phys-
ical and/or chemical.

Adhesives Hot Water Acid Alkali Oil, Grease Fuels Alcohols Ketones Esters Aromatics
Cyanoacrylate 6 6 6 3 3 5 5 5 4

Epoxy + 2 2 2 2 3 1 6 6 1
polyamine
Epoxy + 3 2 2 2 2 6 6 2
anhydride
Epoxy + 6 3 6 2 2 1 6 6 3
polyamide
Acrylic 3 2 2 2 2 2 3 2 3

Acrylate acid 4 6 6 3 3 5 5 5 4
diester
Polyurethane 3 3 3 2 2 2 5 6 -
Silicone (RTV) 2 3 3 2 3 3 3 3 3

Epoxy - 6 2 2 2 2 2 6 6 2
polysulf ide
Epoxy - 2 2 2 3 3 2 6 6 2
phenolic
Table 1: Relative Resistance of ThermosettingAdhesives to Common Chemical Environments'

381 metalfinishing ISeptember2010 www.metalfinishing.com

adhesion
bonding
Physicaldegradation occurs when the
chemical enviro nm en t enters the
molecular network but does not
react with it. For exampl e, liquid
chemicals , solvents, and moisture
can diffus e into a polym er structure
acting as a plasticizer. This action
could cause swelling and dissolution
of the polymer. More importan tly, it
reduces the molecular int eractions
within th e adhesive or adheren d,
and, as a result, properties such as
tensile strength, hardness, elonga-
tion, and heat resistance are adverse-
lyaffected.
Chemical degradation occurs when
the chemical environment causes a
reaction th at results in a breakdown
of the polymer molecule. Th e nature
of this reaction will, of cour se,
depend on the chemistry of th e poly-
mer and the penetrating species.
The effect of moisture, especially at
elevated temperature, is a good
example of this . Water can cause
hydrolysis of certain polymeric mate-
rials. Th is actually breaks the long
polymer mol ecules down into small-
er parts, and th e polymer th at was
once a st rong solid can actu ally be
turned into a gel or liquid state.
Such processes as those described
above can only occur if the chemical
environment is capable of directly
encountering th e adhesive or
adherend molecules to allow interac-
tion. This can be divided into several
steps:
• The sorption of the medium at the
polymer surface
• The diffusion of the medium
through the polymeric material
• The interaction of the polymer and
the diffusing medium
• The diffusion and reaction products
from the polymer bulk to the
interface
Thus, for maximum chemical
resistance it is desirable that the
polymer provides a barri er to the pas-
sage of the chemical med ium int o its
www.metalfinishing.com
structu re. Achieving a good barrier is
often difficult and will depend on
many parameters associated with
both th e adhesive, joint design, and
th e environment.
A measure of the lack of barrier
resistance is generally the permeabil-
ity of species th rough a polymer.
Th is occur s via two processes: solu-
tion and diffusion . Figure 1 illus-
trates th e concepts of solution, dif-
fusion , and permeation. The chemi-
cal must first dissolve (solution) into
th e external surface of th e polymer.
It th en undergoes molecular diffu-
sion through th e polymer.
However, th ese concepts do not
Figure 1. Conceptsof solution,diffusion. and
permeation.
cover all circum stances. Chemicals
or solvents could also enter th e poly-
mer via wicking along reinforcing
fibers or pigments associat ed with
th e formulat ion . This process is
especially evident if th e joi nt is
machined or cut so that adhesive
edges are exposed.
A barrier function can be incorpo -
rated int o an adh esive joint in sever-
al ways:
• Bychoosing a low permeability
Conditions, 77°F after:
30 days in RT water
30 days at 110°F and 100% relat ive humidity
30 days in 95°F sa lt-spray cabinet (5% salt)
7 days in JP-4 jet fuel
7 days in anti -icing fluid (isopropyl alcohol)
7 days in hydraulic oil (Mll-H-5606)
7 days in hydrocarbon test fluid (70/30 vt» isooctane/toluene)
Table 2: Standard Test Fluids and Immersion Conditons for Adhesive Evaluation per MM M-A-132
polymer that is molecularly
engineered to provide good barrier
properties.
• By using appropriate fillers so that
the penetrating species is forced
to take a tortuous path into the
polymer.
• Byexternal protection. (Exposed
joint edges, machined holes, etc.,
can be coated with a high
permeability coating).
In essence, th ere are two ways of
protecting adhesives, sealants, or
coat ings from exposure to chemical
environ ments: a high degree of
crosslinking within the pol ymer
stru ctu re and minimizing the
amount of exposed area th rou gh
design.
TEST METHODS
Cons equences of exposure to chem-
ical environments are so severe that
it is usually necessary to test prepro-
duction joints, both in the laborato-
ry and in the field, under conditions
as close to the actual service envi-
ronment as possible. The parame-
ters th at will likely affect the dura-
bility of a given joint are:
• Maximum stress level
• Average constant stress level
• Nature and type of environment
• Cyclic effects of stress and envi-
ronment (rate and period)
• Time of exposure
In applications where possible
degradin g elements exist, candidate
adhesives must be tested under sim-
ulated service conditions. Imp ortant
information, such as the maximum
load that the adhesive join t will
withstand for extended periods of
time and the degrading effects of
September 2010 I metalfinishing 139
adhesion bonding time are especially vulnerable and
prototype specimens need to be
appropriately tested.
202 3 d, C
5, EPOXY ADHESIVES
When compared to other structur-
~ al adhesives, those based on epoxy
chemistry have outstanding resist-
.to ance to solvents, weak acids, and
.,. alkali compounds. This accounts

I/r ~ - B for their use as adhesives, sealants,

and coatings in many industrial
<,
~
applications. As a result, epoxy
"--- c compounds are used to assemble
water softener tanks, chemical con-
tainers, brewery tanks, and other

, 1'1
-\\ 0

E
industrial components in the
chemical industry.
Epoxy adhesives are generally
more resistant to a wide variety of
C1>
-
I liquid environments than other
I I I I I I I
structural adhesives. However, the
o 4 12 20 2 2 resistance to a specific environment
Expo<$Ure Ii is greatly dependent on the type of
epoxy curing agent used and the for-
Figure 2. Effect of immersion in variouschemical environmentson a one-part heat curingepoxy
adhesive (EA929, Cytec Hysol Division) in (a) gasoline at 75°F, (b)gear oil at 2SQoF, (c) distilled
mulation employed. Generally,
water at 75°F, (d) tap water at 212°F, and (e) Shellzone at 2SQoF.' those factors tending to promote
thermal stability also tend to
improve chemical resistance. So very
various chemical environments, over short time periods. This effect often the adhesives having the great-
must be addressed by several test is possibly due either to post-curing est thermal stability will also provide
methods. or slight plasticizing of the epoxy the greatest chemical resistance.
ASTM D896, "Standard Test by the oil.
Method for Resistance of Adhesive Figure 2 shows the long-term REFERENCES
Bonds to Chemical Reagents", speci- effect of a heat-cured epoxy joint to 1. Weggemans, D. M., "Adhesives
fies the testing of adhesive joints for various chemical environments. As Charts", in Adhesion and Adhesives)
resistance to solvents and chemicals. can be seen, the temperature of the Vol. 2, Elsevier, Amsterdam,
Standard chemical reagents are listed immersion medium is a significant 1967.
in ASTM D543, and the standard factor in the aging properties of the 2. Aerospace Adhesive EA 929,
oils and fuels are given in ASTM adhesive. As the temperature Hysol Division, Dexter Corp.
D471. Standard test fluids and increases, more fluid is absorbed by Tech. Bull.
immersion conditions used by many the adhesive, and the degradation
adhesive suppliers are specified in rate increases.
Military Specification MMM-A-132 The effect of simultaneous expo-
(See Table 2). sure to both mechanical stress and a
Most standard tests to determine chemical environment is often more
chemical resistance of adhesive severe than the sum of each factor
joints last only 30 days or so. taken separately. Mechanical stress,
Unfortunately, exposure tests last- elevated temperatures, and exposure
ing less than 30 days are not appli- to chemicals or solvents can be a fatal BIO
cable to many real-life service combination for certain adhesives Edward M. Petrie isthesale proprietor of
requirements. Practically all adhe- and sealants if all occur at the same EMP Solutions) a Cary) N C.-basedcon-
sives are resistant to these fluids time. The stress can act to accelerate suiting firm focused on solving problems
over short time periods and at room the degradation caused by the envi- in the adhesives and sealants industry.
temperatures. Some epoxy adhe- ronment, and vice versa. Joints that He also works as a technical expertfor
sives even show an increase in will be exposed to both chemical SpecialChem. For more information)
strength during aging in fuel or oil environments and load at the same visitwww.specialchem4adhesives.com.

40 I metalfinishing I September 2010 www.metalfinishing.com