Adhesives, also known as glue, cement, mucilage, or paste, is any
substance applied to one surface, or both surfaces, of two separate
items that binds them together and resists their separation.
Adjectives may be used in conjunction with the word "adhesive" to
describe properties based on the substance's physical or chemical
form, the type of materials joined, or conditions under which it is
The use of adhesives offers many advantages over binding techniques
such as sewing, mechanical fastening, thermal bonding, etc. These
include the ability to bind different materials together, to
distribute stress more efficiently across the joint, the cost
effectiveness of an easily mechanized process, an improvement in
aesthetic design, and increased design flexibility. Disadvantages of
adhesive use include decreased stability at high temperatures,
relative weakness in bonding large objects with a small bonding
surface area, and greater difficulty in separating objects during
testing. Adhesives are typically organized by the method of
adhesion. These are then organized into reactive and non-reactive
adhesives, which refers to whether the adhesive chemically reacts in
order to harden. Alternatively they can be organized by whether the
raw stock is of natural or synthetic origin, or by their starting
Adhesives may be found naturally or produced synthetically. The
earliest human use of adhesive-like substances was approximately
200,000 years ago, when Neanderthals produced tar from the dry
distillation of birch bark for use in binding stone tools to wooden
handles.The first references to adhesives in literature first
appeared in approximately 2000 BC. The Greeks and Romans made great
contributions to the development of adhesives. In Europe, glue was not
widely used until the period AD 1500–1700. From then until the 1900s
increases in adhesive use and discovery were relatively gradual. Only
since the last century has the development of synthetic adhesives
accelerated rapidly, and innovation in the field continues to the
2 Economic importance
3.1 By reactiveness
22.214.171.124 Pre-mixed and frozen adhesives
3.2 By origin
5 Mechanisms of adhesion
6 Methods to improve adhesion
7.1 Cohesive fracture
7.3 Other types of fracture
8 Design of adhesive joints
9 Shelf life
10 See also
12 External links
A reconstruction of Ötzi's axe, which used pitch as an adhesive
The earliest use of adhesives was discovered in central Italy when two
stone flakes partially covered with birch-bark tar and a third
uncovered stone from the Middle Pleistocene era (circa 200,000 years
ago) were found. This is thought to be the oldest discovered human use
of tar-hafted stones.
The birch-bark-tar adhesive is a simple, one-component adhesive.
Although sticky enough, plant-based adhesives are brittle and
vulnerable to environmental conditions. The first use of compound
adhesives was discovered in Sibudu, South Africa. Here,
70,000-year-old stone segments that were once inserted in axe hafts
were discovered covered with an adhesive composed of plant gum and red
ochre (natural iron oxide) as adding ochre to plant gum produces a
stronger product and protects the gum from disintegrating under wet
conditions. The ability to produce stronger adhesives allowed
middle stone age humans to attach stone segments to sticks in greater
variations, which led to the development of new tools.
More recent examples of adhesive use by prehistoric humans have been
found at the burial sites of ancient tribes. Archaeologists studying
the sites found that approximately 6,000 years ago the tribesmen had
buried their dead together with food found in broken clay pots
repaired with tree resins. Another investigation by archaeologists
uncovered the use of bituminous cements to fasten ivory eyeballs to
statues in Babylonian temples dating to approximately 4000 BC.
In 2000, a paper revealed the discovery of a 5,200-year-old man
nicknamed the "Tyrolean Iceman" or "Ötzi", who was preserved in a
glacier near the Austria-Italy border. Several of his belongings were
found with him including two arrows with flint arrowheads and a copper
hatchet, each with evidence of organic glue used to connect the stone
or metal parts to the wooden shafts. The glue was analyzed as pitch,
which requires the heating of tar during its production. The retrieval
of this tar requires a transformation of birch bark by means of heat,
in a process known as pyrolysis.
The first references to adhesives in literature first appeared in
approximately 2000 BC. Further historical records of adhesive use are
found from the period spanning 1500–1000 BC. Artifacts from this
period include paintings depicting wood gluing operations and a casket
made of wood and glue in King Tutankhamun's tomb. Other ancient
Egyptian artifacts employ animal glue for bonding or lamination. Such
lamination of wood for bows and furniture is thought to have extended
their life and was accomplished using casein (milk protein)-based
glues. The ancient Egyptians also developed starch-based pastes for
the bonding of papyrus to clothing and a plaster of Paris-like
material made of calcined gypsum.
From AD 1 to 500 the Greeks and Romans made great contributions to the
development of adhesives. Wood veneering and marquetry were developed,
the production of animal and fish glues refined, and other materials
utilized. Egg-based pastes were used to bond gold leaves incorporated
various natural ingredients such as blood, bone, hide, milk, cheese,
vegetables, and grains. The Greeks began the use of slaked lime as
mortar while the Romans furthered mortar development by mixing lime
with volcanic ash and sand. This material, known as pozzolanic cement,
was used in the construction of the Roman Colosseum and Pantheon.
The Romans were also the first people known to have used tar and
beeswax as caulk and sealant between the wooden planks of their boats
Modern slaked lime factory in Ukraine
In Central Asia, the rise of the
Mongols in approximately AD 1000 can
be partially attributed to the good range and power of the bows of
Genghis Khan's hordes. These bows were constructed with laminated
lemonwood and bullhorn bonded by an unknown adhesive.
In Europe, glue fell into disuse until the period AD 1500–1700. At
this time, world-renowned cabinet and furniture makers such as Thomas
Duncan Phyfe began to use adhesives to hold their
The development of modern adhesives began in 1690 with the founding of
the first commercial glue plant in Holland. This plant produced glues
from animal hides.
Liquid animal glue
In 1750, the first British glue patent was issued for fish glue. The
following decades of the next century witnessed the manufacture of
casein glues in German and Swiss factories. In 1876, the first US
patent (number 183,024) was issued to the Ross brothers for the
production of casein glue.
Casein glue preparation
The first US postage stamps used starch-based adhesives when issued in
1840. The first US patent (number 61,991) on dextrin (a starch
derivative) adhesive was issued in 1867.
Natural rubber was first used as material for adhesives starting in
1830. In 1839,
Charles Goodyear discovered that a rubber and
sulfur mixture, when heated, becomes elastic. In 1843, Thomas Hancock
named this process vulcanization. In 1862, a British patent (number
3288) was issued for the plating of metal with brass by
electrodeposition to obtain a stronger bond to rubber. The
development of the automobile and the need for rubber shock mounts
required stronger and more durable bonds of rubber and metal. This
spurred the development of cyclized rubber treated in strong acids. By
1927, this process was used to produce solvent-based thermoplastic
rubber cements for metal to rubber bonding.
Natural rubber-based sticky adhesives were first used on a backing by
Henry Day (US Patent 3,965) in 1845. Later these kinds of
adhesives were used in cloth backed surgical and electric tapes. By
1925, the pressure-sensitive tape industry was born. Today, sticky
notes, Scotch tape, and other tapes are examples of PSA
A key step in the development of synthetic plastics was the
introduction of a thermoset plastic known as
Bakelite phenolic in
1910. Within two years, phenolic resin was applied to plywood as a
coating varnish. In the early 1930s, phenolics gained importance as
The 1920s, 1930s, and 1940s witnessed great advances in the
development and production of new plastics and resins due to the First
and Second World Wars. These advances greatly improved the development
of adhesives by allowing the use of newly developed materials that
exhibited a variety of properties. With changing needs and ever
evolving technology, the development of new synthetic adhesives
continues to the present. However, due to their low cost, natural
adhesives are still more commonly used.
In the course of time and during their development, adhesives have
gained a stable position in an increasing number of production
processes. There is hardly any product in our surroundings that does
not contain at least one adhesive—be it the label on a beverage
bottle, protective coatings on automobiles, or profiles on window
frames. Market researchers forecast a turnover of almost US$50 billion
for the global adhesives market in 2019. In particular, the economic
development of emerging countries such as China, India, Russia, and
Brazil will cause a rising demand for adhesives in the future.
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See also: List of glues
Adhesives are typically organized by the method of adhesion. These are
then organized into reactive and non-reactive adhesives, which refers
to whether the adhesive chemically reacts in order to harden.
Alternatively they can be organized by whether the raw stock is of
natural, or synthetic origin, or by their starting physical phase.
There are two types of adhesives that harden by drying: solvent-based
adhesives and polymer dispersion adhesives, also known as emulsion
adhesives. Solvent-based adhesives are a mixture of ingredients
(typically polymers) dissolved in a solvent. White glue, contact
adhesives and rubber cements are members of the drying adhesive
family. As the solvent evaporates, the adhesive hardens. Depending on
the chemical composition of the adhesive, they will adhere to
different materials to greater or lesser degrees.
Polymer dispersion adhesives are milky-white dispersions often based
on polyvinyl acetate (PVAc). They are used extensively in the
woodworking and packaging industries. They are also used with fabrics
and fabric-based components, and in engineered products such as
Main article: Pressure-sensitive adhesive
Pressure-sensitive adhesives (PSA) form a bond by the application of
light pressure to marry the adhesive with the adherend. They are
designed to have a balance between flow and resistance to flow. The
bond forms because the adhesive is soft enough to flow (i.e., "wet")
to the adherend. The bond has strength because the adhesive is hard
enough to resist flow when stress is applied to the bond. Once the
adhesive and the adherend are in close proximity, molecular
interactions, such as van der Waals forces, become involved in the
bond, contributing significantly to its ultimate strength.
PSAs are designed for either permanent or removable applications.
Examples of permanent applications include safety labels for power
equipment, foil tape for
HVAC duct work, automotive interior trim
assembly, and sound/vibration damping films. Some high performance
permanent PSAs exhibit high adhesion values and can support kilograms
of weight per square centimeter of contact area, even at elevated
temperatures. Permanent PSAs may initially be removable (for example
to recover mislabeled goods) and build adhesion to a permanent bond
after several hours or days.
Removable adhesives are designed to form a temporary bond, and ideally
can be removed after months or years without leaving residue on the
adherend. Removable adhesives are used in applications such as surface
protection films, masking tapes, bookmark and note papers, barcodes
labels, price marking labels, promotional graphics materials, and for
skin contact (wound care dressings, EKG electrodes, athletic tape,
analgesic and transdermal drug patches, etc.). Some removable
adhesives are designed to repeatedly stick and unstick. They have
low adhesion, and generally cannot support much weight.
Pressure-sensitive adhesive is used in Post-it notes.
Pressure-sensitive adhesives are manufactured with either a liquid
carrier or in 100% solid form. Articles are made from liquid PSAs by
coating the adhesive and drying off the solvent or water carrier. They
may be further heated to initiate a cross-linking reaction and
increase molecular weight. 100% solid PSAs may be low viscosity
polymers that are coated and then reacted with radiation to increase
molecular weight and form the adhesive, or they may be high viscosity
materials that are heated to reduce viscosity enough to allow coating,
and then cooled to their final form. Major raw material for PSA's are
Contact adhesives are used in strong bonds with high shear-resistance
like laminates, such as bonding Formica to a wooden counter, and in
footwear, as in attaching outsoles to uppers.
Natural rubber and polychloroprene (Neoprene) are commonly used
contact adhesives. Both of these elastomers undergo strain
crystallization. In the construction industry a specialised
proprietary adhesive known as "liquid nails" is used. This also
copes with tasks such as sealing artificial turf.
Contact adhesives must be applied to both surfaces and allowed some
time to dry before the two surfaces are pushed together. Some contact
adhesives require as long as 24 hours to dry before the surfaces are
to be held together. Once the surfaces are pushed together, the
bond forms very quickly. It is usually not necessary to apply
pressure for a long time, so there is less need for clamps.
A glue gun, an example of a hot adhesive
Main article: Hot-melt adhesive
Hot adhesives, also known as hot melt adhesives, are thermoplastics
applied in molten form (in the 65–180 °C range) which solidify
on cooling to form strong bonds between a wide range of materials.
Ethylene-vinyl acetate-based hot-melts are particularly popular for
crafts because of their ease of use and the wide range of common
materials they can join. A glue gun (shown at right) is one method of
applying hot adhesives. The glue gun melts the solid adhesive, then
allows the liquid to pass through its barrel onto the material, where
Thermoplastic glue may have been invented around 1940 by Procter &
Gamble as a solution to the problem that water-based adhesives,
commonly used in packaging at that time, failed in humid climates,
causing packages to open.
Multi-component adhesives harden by mixing two or more components
which chemically react. This reaction causes polymers to
cross-link into acrylics, urethanes, and epoxies - See
There are several commercial combinations of multi-component adhesives
in use in industry. Some of these combinations are:
Polyester resin – polyurethane resin
Polyols – polyurethane resin
Acrylic polymers – polyurethane resins
The individual components of a multi-component adhesive are not
adhesive by nature. The individual components react with each other
after being mixed and show full adhesion only on curing. The
multi-component resins can be either solvent-based or solvent-less.
The solvents present in the adhesives are a medium for the polyester
or the polyurethane resin. The solvent is dried during the curing
Pre-mixed and frozen adhesives
Pre-mixed and frozen adhesives (PMFs) are adhesives that are mixed,
deaerated, packaged, and frozen. As it is necessary for PMFs to
remain frozen before use, once they are frozen at -80 °C they are
shipped with dry ice and are required to be stored at or below -40
°C. PMF adhesives eliminate mixing mistakes by the end user and
reduce exposure of curing agents that can contain irritants or
toxins. PMFs were introduced commercially in the 1960s and are
commonly used in aerospace and defense.
One-part adhesives harden via a chemical reaction with an external
energy source, such as radiation, heat, and moisture.
Ultraviolet (UV) light curing adhesives, also known as light curing
materials (LCM), have become popular within the manufacturing sector
due to their rapid curing time and strong bond strength. Light curing
adhesives can cure in as little as a second and many formulations can
bond dissimilar substrates (materials) and withstand harsh
temperatures. These qualities make
UV curing adhesives essential to
the manufacturing of items in many industrial markets such as
electronics, telecommunications, medical, aerospace, glass, and
optical. Unlike traditional adhesives, UV light curing adhesives not
only bond materials together but they can also be used to seal and
coat products. They are generally acrylic-based.
Heat curing adhesives consist of a pre-made mixture of two or more
components. When heat is applied the components react and cross-link.
This type of adhesive includes thermoset epoxies, urethanes, and
Moisture curing adhesives cure when they react with moisture present
on the substrate surface or in the air. This type of adhesive includes
cyanoacrylates and urethanes.
See also: List of polyurethane applications § Adhesives
Natural adhesives are made from organic sources such as vegetable
starch (dextrin), natural resins, or animals (e.g. the milk protein
casein and hide-based animal glues). These are often referred to
One example is a simple paste made by cooking flour in water.
Starch-based adhesives are used in corrugated board and paper sack
production, paper tube winding, and wallpaper adhesives.
is mainly used to adhere glass bottle labels. Animal glues have
traditionally been used in bookbinding, wood joining, and many other
areas but now are largely replaced by synthetic glues except in
specialist applications like the production and repair of stringed
Albumen made from the protein component of blood has been
used in the plywood industry. Masonite, a wood hardboard, was
originally bonded using natural wood lignin, an organic polymer,
though most modern particle boards such as MDF use synthetic
Synthetic adhesives are based on elastomers, thermoplastics,
emulsions, and thermosets. Examples of thermosetting adhesives are:
epoxy, polyurethane, cyanoacrylate and acrylic polymers. The first
commercially produced synthetic adhesive was Karlsons Klister in the
Applicators of different adhesives are designed according to the
adhesive being used and the size of the area to which the adhesive
will be applied. The adhesive is applied to either one or both of the
materials being bonded. The pieces are aligned and pressure is added
to aid in adhesion and rid the bond of air bubbles.
Common ways of applying an adhesive include brushes, rollers, using
films or pellets, spray guns and applicator guns (e.g., caulk gun).
All of these can be used manually or automated as part of a machine.
Mechanisms of adhesion
Main article: Adhesion
For an adhesive to be effective it must have three main properties. It
must be able to wet the substrate. It must harden [note: not all
adhesives harden] and finally it must be able to transmit load between
the two surfaces/substrates being adhered.
Adhesion, the attachment between adhesive and substrate may occur
either by mechanical means, in which the adhesive works its way into
small pores of the substrate, or by one of several chemical
mechanisms. The strength of adhesion depends on many factors,
including the means by which it occurs.
In some cases, an actual chemical bond occurs between adhesive and
substrate. In others, electrostatic forces, as in static electricity,
hold the substances together. A third mechanism involves the van der
Waals forces that develop between molecules. A fourth means involves
the moisture-aided diffusion of the glue into the substrate, followed
Methods to improve adhesion
The quality of adhesive bonding depends strongly on the ability of the
adhesive to efficiency cover (wet) the substrate area. This happens
when the surface energy of the substrate is greater than the surface
energy of the adhesive. However, high strength adhesives have high
surface energy. Thus, their application is problematic for low energy
materials such as polymers. To solve this problem, surface treatment
can be used to increase the surface energy as a preparation step
before adhesive bonding. Importantly, surface preparation provides a
reproducible surface allowing consistent bonding results. The commonly
used surface activation techniques include plasma activation, flame
treatment and wet chemistry priming.
Failure of the adhesive joint can occur in different locations
There are several factors that could contribute to the failure of two
adhered surfaces. Sunlight and heat may weaken the adhesive. Solvents
can deteriorate or dissolve adhesive. Physical stresses may also cause
the separation of surfaces. When subjected to loading, debonding may
occur at different locations in the adhesive joint. The major fracture
types are the following:
Cohesive fracture is obtained if a crack propagates in the bulk
polymer which constitutes the adhesive. In this case the surfaces of
both adherends after debonding will be covered by fractured adhesive.
The crack may propagate in the center of the layer or near an
interface. For this last case, the cohesive fracture can be said to be
"cohesive near the interface".
Adhesive fracture (sometimes referred to as interfacial fracture) is
when debonding occurs between the adhesive and the adherend. In most
cases, the occurrence of adhesive fracture for a given adhesive goes
along with smaller fracture toughness.
Other types of fracture
Other types of fracture include:
The mixed type, which occurs if the crack propagates at some spots in
a cohesive and in others in an interfacial manner. Mixed fracture
surfaces can be characterised by a certain percentage of adhesive and
The alternating crack path type which occurs if the cracks jump from
one interface to the other. This type of fracture appears in the
presence of tensile pre-stresses in the adhesive layer.
Fracture can also occur in the adherend if the adhesive is tougher
than the adherend. In this case, the adhesive remains intact and is
still bonded to one substrate and remnants of the other. For example,
when one removes a price label, the adhesive usually remains on the
label and the surface. This is cohesive failure. If, however, a layer
of paper remains stuck to the surface, the adhesive has not failed.
Another example is when someone tries to pull apart
Oreo cookies and
all the filling remains on one side; this is an adhesive failure,
rather than a cohesive failure.
Design of adhesive joints
Modes of failure
As a general design rule, the material properties of the object need
to be greater than the forces anticipated during its use. (i.e.
geometry, loads, etc.). The engineering work will consist of having a
good model to evaluate the function. For most adhesive joints, this
can be achieved using fracture mechanics. Concepts such as the stress
concentration factor and the strain energy release rate can be used to
predict failure. In such models, the behavior of the adhesive layer
itself is neglected and only the adherents are considered.
Failure will also very much depend on the opening mode of the joint.
Mode I is an opening or tensile mode where the loadings are normal to
Mode II is a sliding or in-plane shear mode where the crack surfaces
slide over one another in direction perpendicular to the leading edge
of the crack. This is typically the mode for which the adhesive
exhibits the highest resistance to fracture.
Mode III is a tearing or antiplane shear mode.
As the loads are usually fixed, an acceptable design will result from
combination of a material selection procedure and geometry
modifications, if possible. In adhesively bonded structures, the
global geometry and loads are fixed by structural considerations and
the design procedure focuses on the material properties of the
adhesive and on local changes on the geometry.
Increasing the joint resistance is usually obtained by designing its
geometry so that:
The bonded zone is large
It is mainly loaded in mode II
Stable crack propagation will follow the appearance of a local
Some glues and adhesives have a limited shelf life. Exposure to heat,
oxygen, water vapor, etc. can degrade the adhesive over time,
preventing it from functioning properly.
Adhesive surface forces
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