How Sealants Function

How do the application and performance characteristics of

sealants correlate to the composition of the sealant
formulation?

One-part silicones are used in bathtub applications.

Table 1. Typical Applications for Sealants 1
Table 2. Checklist of Considerations for the Selection of Construction Sealants 2
One-part silicones are used in sink applications.
February 27, 2006
Edward M. Petrie
KEYWORDS sealants in aerospace / sealants in assembly / sealants in
automotive / sealants in construction / sealants in electrical/electronic / sealants in
transportation
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Sealants are generally chosen for their ability to fill gaps, resist relative movement of
the substrates, and exclude or contain another material. Sealants are generally lower in
strength than adhesives, but have better flexibility. Usually, a sealant must effectively
bond to a substrate in order to perform these functions.

Sealants are like adhesives in many ways. If fact, they are often considered to be
together because some formulations can perform as either an adhesive or as a sealant,
and some formulations actually provide both functions. Sealants, however, must
perform distinctive tasks that put them in a separate category from adhesives. It is
important that the sealant formulator recognizes and adjusts to suit these functional
needs.

This article will review the special functions required of sealants. The methods by
which the sealant performs these functions will be reviewed. Specifically, the
application and performance characteristics of sealants will be addressed and
correlated to the composition of the sealant formulation.

Functions of Sealants
Sealants are generally used as a barrier or a means of protection. In this way, sealants
are used to exclude dust, dirt, moisture and chemicals, or to contain a liquid or gas.
They are also often used as a coating to protect a surface or an article. They can
eliminate noise and vibration, improve appearance, and perform a joining function.
Sealants can also be used as electrical or thermal insulators and fire barriers, and they
may also be used for smoothing or filleting. Indeed, sealants are often called upon to
perform several of these functions at once.

No matter what the application, a sealant has three basic functions.

1. It fills a gap between two or more substrates.

2. It forms a barrier through the physical properties of the sealant itself and by
adhesion to the substrate.
3. It maintains sealing properties for the expected lifetime, service conditions and
environments.

The sealant performs these functions by way of correct formulation to achieve specific
application and performance properties. These properties are discussed in the
following sections.

Unlike adhesives, there are not many functional alternatives to the sealing process.
Soldering or welding can perhaps be used as a sealant in certain instances, depending
on the substrates and the relative movement that the substrates will see in service.
However, the simplicity and reliability offered by organic elastomers usually make
them the clear choice for performing these functions.

Many sealants are designed for specific applications. Table 1 gives typical
applications for various classes of sealants. The proper application of a sealant
involves more than merely choosing a material with the correct physical and chemical
properties. As with adhesives, the substrates to be sealed, the joint design,
performance expectations, production requirements and economic costs must all be
considered. Table 2 offers a partial list of considerations that are often used to select
sealants in the construction industry.

Application Properties
The speed at which a sealant cures is crucial in some industries. Catalytic primers,
two-component systems or controlled environments are used to increase cure rates.
Depth of cure and the rate at which cure is achieved throughout the joint are other
important considerations. Single-component sealants, such as silicones, urethanes and
polysulfides, which depend on the diffusion of atmospheric moisture or oxygen into
the sealant for curing, can take days or even weeks to cure entirely throughout the
sealant bead. These sealants will develop a skin that will then inhibit the diffusion of
water vapor to the center regions of the seal. In fact, some of these systems are limited
to very small cross-sectional beads; otherwise they will never fully cure throughout.
Shrinkage on curing can be a crucial factor for sealant systems as well as adhesives.
Excessive shrinkage can result in internal stresses and voids in the joint. Low-
shrinkage products are those with very high or 100% solids, such as many of the two-
component systems. Medium-shrinkage systems include hot-melt sealants that shrink
as they go from a molten state to a gelatinous state. High-shrinkage systems are all
solvent- or aqueous-based sealants in which shrinkage offers due to evaporation of
solvent or water.

For improved gap-filling characteristics, some sealants are formulated to expand prior
to curing. These sealants include automotive sealants with foaming agents in the
formulation similar to the foaming agents used in packaging materials. Hot-melt
formulations are also prepared with gases dissolved into the resin that will expand
when heated. All of these formulations will expand before cure to fill in the joint gap
and maintain positive pressure on the substrate as the sealant cures.

Foam-in-place gaskets promise to eliminate production bottlenecks in mass-produced

automobiles, appliances, electronics and office equipment. These sealants are either
hot-melt thermoplastic (e.g., ethylene vinyl acetate, butyl) or multicomponent curable
thermosets (e.g., urethane). These materials can be applied directly to the joint, thus
eliminating the need for die-cut gaskets and the resulting large quantities of scrap.
Preformed solid gaskets conserve material but are labor-intensive and require
secondary adhesives to install. In addition, because it can be applied in three
dimensions, foam-in-place gasketing provides greater flexibility in joint design.

The sealant must wet the substrate and easily flow into the joint; therefore, it must be
a liquid during application. However, if it is to remain in a vertical joint, it must
behave as a solid. The former condition is met by using a liquid polymer or a solution
of a solid polymer. In either case, the flow properties of the liquid must be such that
flow is reasonable under a moderately applied stress, but ceases when the stress is
small. This requirement is called thixotropy, flow control or anti-slump. It is obtained
in sealant formulations generally by fillers if the base polymer is a liquid, or by
solvents when the polymer is a solid.

When working with sealants, joint design considerations, such as crack bridging,
coverage rates, color, practicality of placement, order of placement, unusual
movement conditions, and aesthetics, must be addressed. One consideration that is
required of sealants (but not generally adhesives) is appearance. A sealant material
may be acceptable in all respects, but appearance problems could make it aesthetically
unacceptable. Usually, sealants are easily visible whether the application is in the
automotive, construction or appliance industries. Adhesives, on the other hand, are
often hidden by the substrates. The sealant could also contain compounds that discolor
surrounding areas. They can also be incorrectly applied so that the flow of liquids in
contact with the sealant results in a residual buildup of extraneous matter at the joint.

An important consideration for any sealing operation is the relative ease of handling
and applying the sealant. There are wide ranges of sealants available with varying
degrees of application difficulty (single- and two-component sealants, primer and
primerless sealant systems, hot-melt application systems, and sealants containing
solvents). As with adhesives, the time required for the sealant to harden from a liquid
into a semi-solid with some degree of handling strength is very important. Significant
production properties include: cure rate, low-temperature flow characteristics, paint-
over ability, color, self-leveling properties, non-bubbling properties, and cost.

Safety and toxicity effects are a concern when using certain types of sealants.
Chemical reactions can cause the release of toxic fumes, heat, or possibly both.
Solvent evaporation may contribute to a safety or heath hazard in the working place.
Metering and mixing of multiple-component systems could bring personnel into direct
contact with the components, resulting in dermatitis or other health-related problems.

Performance Properties
Important mechanical properties of sealants include elongation, compressibility, and
tensile strength, modulus of elasticity, tear resistance and fatigue resistance.
Depending on the nature of the application, a sealant may require very little strength
or great strength. The sealant must have sufficient mechanical characteristics to
remain attached to substrates during service as well as to provide a barrier. The
substrates could move considerably, requiring that the sealant expand and contract
significantly without losing adhesion from the surface. Defining movement capability
is a complex process. Temperature, rate of temperature change and joint configuration
will influence the results.

In some applications, strength may be more important than elasticity. Low-strength or

- more precisely - low tensile modulus may be the most important factor in a situation
where a sealant joins one or more weak surfaces. Tensile strength is needed primarily
to avoid cohesive failure under stress and so as not to transfer stress between
substrates, as is the case with most adhesives.

Modulus can sometimes predict the extension or compression characteristics of a

sealant. Generally, low-to-medium-modulus sealants are able to take significant
movement without putting much stress on the sealant or the substrate materials. Some
high-performance sealants are formulated for a higher movement capability than a
joint is actually designed to accommodate. In fact, joints designed for about 25%
extension/compression must often accommodate movement of 50% or more. Thus,
higher- performance sealants provide an added safety factor. A change in elasticity or
hardness on aging may be an indication that further curing or degradation is taking
place.

Compressive strength is the maximum compressive stress that a sealant can withstand
without breaking down or experiencing excessive extrusion from the joint.
Compression set is the inability of a sealant to return to its original dimension after
being compressed. High compression set is usually caused by further curing or
degradative crosslinking of the material while under compression. Compression set is
undesirable in a joint that needs to expand and contract. Stress relaxation is a
condition in which the stress decays as the strain remains constant. Some very-low-
modulus sealants literally get pulled apart when held at low elongation.

Sealants may be exposed to scuffing and mechanical wear. Examples include the
sealant used as an expansion joint in the highway and the sealant used in preparing
stone walkways. Thus, they must offer good abrasion, puncture and tear resistance.
Flexible sealants, which are available in either chemical curing or non-curing types,
exhibit varying degrees of tear resistance. Urethanes have the highest tear resistance.
Dynamic loads, shock, and rapid variations in stress can also cause seals to fail. Thus,
the consideration of tough and flexible elastomeric sealants that can stretch and then
return to their original length in a short time should be the first step in the selection
process for joints designed for mechanical loads.

Adhesion is also an important factor in determining a sealant's performance. The same

rules of adhesion that apply to adhesives also apply to sealants. Adhesion is primarily
affected by the physio-chemical interaction between the sealant material and the
surface to which it is applied. However, in certain joints where there is great
movement, strong adhesion of a sealant to a specific substrate may not be desirable. In
these situations, the adhesive strength is stronger than the cohesive strength of the
sealant, and the sealant may tear apart when it expands or contracts. This requires the
sealant to be applied so that it does not adhere to all surfaces. To achieve this affect, a
bond-breaker or release material at the bottom of the joint is generally used.

Conditions that will influence the adhesion of sealants include water exposure,
temperature extremes, movement considerations and surface cleanliness. Often, a
surface-conditioning process or a priming step is necessary to make a substrate
compatible with a specific sealant.

Weatherability is defined as a sealant's degree of resistance when exposed to heat,

moisture, cold, solar radiation, etc. The degree of weatherability is determined by the
base polymer and the nature of the additives in the sealant formulation. Generally,
sealants are formulated for maximum resistance to a single element, such as moisture.
Often, this chemistry will lend its resistance to other elements as well.

In many situations, the appearance of the sealant is almost as important as its physical
properties. Thus, most sealants are available in a variety of colors to match the
environment in which they are used. Several questions must be considered when
determining the appearance requirements of sealants.

 Does a sealant cause discoloration of surrounding areas initially or over a

period of time?
 Does water runoff over the material cause unsightly residues?
 Does one product cause discoloration of another?
 Does the product itself change in appearance over time for any reason?

Sealants can have a chemical effect on the substrate. Chemical incompatibility could
cause the sealant or substrate to soften, harden, crack, craze, inhibit cure, or cause
other changes. An example of this would be the use of an acid cure sealant (such as a
silicone sealant) on a surface like concrete, marble, or limestone. On these surfaces,
an acid/base reaction can cause the formation of bond-breaking salts at the bond-line.
Another example of chemical incompatibility is the bleed of plasticizers or other low-
molecular-weight volatiles through sealants, causing them to discolor after exposure
to sunlight. This happens frequently when sealants or coatings are applied over
asphalt or organic rubber-based materials that are formulated with low-molecular-
weight plasticizers.

Sealants may also need to be compatible with a specific environment for certain
applications. Examples of this may be a requirement for a sealant to have USDA or
FDA acceptance because food or drugs are to be processed in the area near the
sealant. It may happen that, in an installation such as a food processor or clean room,
the sealant cannot outgas or liberate certain chemical components either during or
after cure. Another end-use requirement could be that the sealant must meet certain
fire-resistance properties to meet code requirements in housing construction or
another area of use.
Formulations
A range of materials and formulations is available for preparing sealant products that
meet a specific need. Most sealants, however, are compromise formulations. That is,
manufacturers formulate their products to meet a variety of applications. These
products, then, meet a majority of needs, while the final choice rests with the
informed user. Most sealants are capable of meeting a variety of standards relative to
joint movement and other properties.

Modern demands for increased productivity, higher performance and environmentally

safer materials have led to a decline in the use of some of the older chemistries,
particularly solvent-based sealants. Over the past several years, polyurethanes have
become one of the mainstays for the sealing of building joints. Silicones have had
success in structural glazing applications due to their favorable performance in
weathering, particularly UV resistance. During this time, polysulfides have been
losing ground.

Like adhesives, sealant formulations contain a base polymer that is modified by many
possible extenders and adders. However, sealant formulations are usually more
complex than adhesive formulations because of the many compromises that must be
made regarding application, curing and performance characteristics. The sealant's
material cost is also often an important criterion for certain industries because of the
high volumes of material that are be used.

Modern sealants are generally formulated from synthetic elastomeric polymers. Many
of these modern sealants were commercially unavailable before the early 1960s. Some
of the polymers that have been used to formulate sealants include polysulfides,
polyurethanes, chloroprenes, acrylic, and butyl and chlorosulfonated polyethylene.
Like adhesive systems, sealant formulations contain base polymer, fillers, plasticizers,
thixotropic agents, adhesion promoters, catalysts, curing agents and other ingredients.
Various external accessory materials, such as primers, bond-breaker tapes, back-up
materials, and other aids, may also be needed during the application stage to provide
for an effective sealant joint.

Many other additives similar to adhesive system additives are used for sealant
formulation to provide special performance, application, or storage properties. For
example, antibacterial agents and freeze-thaw cycle suppressants are commonly used
in water-based sealant formulations, as well as with adhesives. Many sealant additives
are required to accommodate long-term outdoor exposure or color matching. Sealant
formulations may also include UV absorbers and ozone inhibitors, to prevent any
undesirable sensitivity to outdoor environments. Linear hydrocarbon rubbers are
especially sensitive to sunlight and ozone, and are generally used only for indoor
applications.

If a sealant's long-term performance and weather ability are important to an

application, contact the sealant manufacturer and ask for the results of accelerated
testing performed for their sealants on specific substrates and under specific loading
and environmental conditions. Such data are often available and can identify at least a
family of sealants that may be candidates for the application.

References

1. Panek, J.R.; Cook, J.P., Chapter 2, Construction Adhesives and Sealants, John
Wiley & Sons, New York, 1991.
2. Dunn, D.J., “Sealants and Sealant Technology,” Engineered Materials
Handbook, Vol 3: Adhesives and Sealants, ASM International, 1990.