Adhesion and Adhesives (Read)

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Adhesion and adhesives
Introduction
Adhesives have been in use for several thousands of years. Broken pottery repaired with
pine rosin, the first known hot melt, has been found in the tombs of the ancient Kings
of Egypt. The earliest known application of animal glues dates back to 1500BC and the
early adhesives used by mankind were, of course, based on natural products such as
animal glues, tree rosin, starch, latex rubber and casein. Indeed, these are still used in
both their simple and modified forms. Synthetic glues were not introduced until the
1940s but developments since then have been many fold. For example, corrugated
board which was once bonded with the mineral-based sodium silicate adhesive is now
glued with resin-modified starches which produce a softer, more flexible joint. The
starch–dextrin glues used for carton production have largely been replaced with poly-
vinyl acetate emulsion adhesives. The development of new adhesives has gone hand-in-
hand with that of synthetic polymers. Adhesives invariably comprise thermoplastic or
cross-linking polymers.
Today, adhesives are used for a wide range of applications in which they are required
to bond an even wider range of materials. From bookbinding to packaging, ceramics to
aircraft structures, from woodworking to car bodies, adhesives play a major role, and
high-tech applications have demanded the development of high-tech adhesives. In the
print-related industries we may concentrate on print finishing and converting processes
such as bookbinding and packaging requirements for sealing and joining paper, board
and plastic films. However, just as the range of substrate materials and product require-
ments is wide, so is the arsenal of adhesives which have been developed to satisfy them.
Principles of adhesives
The concepts of wetting and surface energy applied to adhesion and cohesion in
Chapter 7 are further developed, to examine the theories of adhesion, at the end of this
chapter. At this point we only attempt to to explore the conditions necessary for good
adhesion to occur. In general we are concerned with bonding two surfaces, which are
called the adherends, by indirect contact with an intermediate material, the adhesive.
The result is a sandwich of adhesive between the two surfaces to be bonded. The success
of the bond depends on two factors:
● Close molecular contact between the adherend and the adhesive. The distance
between molecules of the two must be less than 0.5nm for the forces of adhe-
sion to come into play. In fact no two solids can get this close because most
surfaces have a roughness of at least several hundred nanometres. In order to
make close enough contact, at least one surface must deform to fit the other.
Since this is impracticable for solids, the role of the adhesive is to flow into the
minute troughs and irregularities of the two adherend surfaces, forming a bridg-
ing bond between them.
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298 Printing materials: science and technology
● The second requirement for good adhesion is that the adhesive completely wets
the minute contours of the adherend surfaces. This can only happen if the sur-
face energy of the adherend is higher than that of the adhesive (Chapter 7).
Figure 12.1 illustrates the condition of (a) perfect wetting when all surfaces of
the two adherends are in contact with adhesive; (b) poor wetting when the liq-
uid has a high contact angle with the adherends; and (c) a common situation
when only one adherend surface is wetted.
(a)
(b)
(c)
Figure 12.1: Adherend wetting: (a) good wetting; (b) poor wetting; (c) only one adherend
surface has been wetted by the adhesive
Polymers such as those used in flexible packaging present wettability problems

because many modern adhesives are themselves based on the same or similar polymer
types and therefore have similar surface energies. As a simple rule of thumb, the surface
energies (tensions) of adherend and adhesive should differ by at least 10mNm–1 to be
sure of good wetting. Reference to Figure 12.2 indicates the nature of the problem in
that substrate materials such as PVC, polystyrene, polyester and acetal have surface
energies of the same order of magnitude as epoxy, polyurethane and cyanoacrylate-
based adhesives. Polymers in Table 12.1 are arranged in order of increasing surface
energy and therefore of increasing ease of bonding for a given adhesive. The surface
energies of these polymers may be increased by up to 20% by modifying the chemical
structure of their surfaces using a corona discharge or flame treatment.
Thus the strength of the bond depends upon the nature of the molecules in contact at
the boundary. The more polar are the molecules that lie in the surface of the adherend,
the easier it is to wet and bond with a polar liquid adhesive. A simple demonstration of
adhesion is to sandwich a drop of water between two clean glass slides. The polar silicate
(SiO3) groups in the glass surface (surface energy 75 mN m–1) attract the polar (OH)
groups in water (surface tension 72.6mNm–1) causing it to spread and wet. The second
glass slide brought into contact experiences similar attractive forces with the water. The
two glass slides are bonded by the water and cannot easily be pulled apart.
Water is therefore a suitable adhesive for bonding glass, or rather it would be if it
could be made to solidify and give a permanent bond. The third requirement for an adhe-
sive then is that it can solidify after the bond has been made. The method of solidification
will depend on the nature of the adhesive and that of the surface to be bonded. Overall, if
Adhesion and adhesives 299
Surface energy (mNm–1)

Solids Liquids
80
water-based adhesives
70
60
Nylon 50
40
PVC, polystyrene epoxy
Adherends polyurethane
polyester (linear) acetal adhesives
cyanoacrylate
30
Teflon 20
Figure 12.2: Relative surface energies (tensions) of adherend and adhesive types
Table 12.1: Surface energies of polymer substrates

Polymer Surface energy (mN m–1)
Polytetraflouroethane (PTFE) 19
Silicon polydimethylene 24
Polythene 31
Polypropylene 31
Natural rubber 31
Polystyrene 33
Polyurethane 38
Polyvinyl acetate 38
Polymethylmethacrylate (perspex) 39
Polyvinyl chloride (PVC) 39
Polyvinylidene chloride 40
Nylon 6,6 43
Polycarbonate 44
Polyester 51
Bakelite 51
Urea–formaldehyde 61
wetting has taken place, bond strength should be maximized when solidification is com-
plete. However, the strength of the bond is never greater than the strength of the weakest
surface it is in contact with.
Another factor that appears to influence the adhesion properties of an adhesive is the
molecular mass of the polymer used. Figure 12.3 indicates that, whereas cohesion
increases with molecular mass, adhesion first peaks and then diminishes. Since viscosity
is a function of molecular mass, it is to be expected that increasing the viscosity of the
polymer system reduces the ability of an adhesive to wet an adherend.
Cohesion
Property
Adhesion
Molecular mass
Figure 12.3: The variation of cohesion and adhesion with molecular mass
Operating parameters for adhesives
Before considering the different classes of adhesives in use, it is necessary to identify the
parameters that must be considered in the application technology. The economics of
using adhesives industrially require low costs not just for the materials used but for the
methods of substrate application themselves. Thus, the factors contributing to high pro-
cessing speeds, such as fast setting times, compact and simple applicators, clean hand-
ling and ease of cleaning up equipment, are all important considerations. Whatever the
type of adhesive being applied, the following parameters must be considered.
Open time
This is the time interval, after application of the adhesive film to the first surface, during
which it remains sufficiently liquid to allow the second surface to be bonded satisfacto-
rily to the first. One mechanism that all types of adhesive have in common after applica-
tion, is a rise in viscosity and tack of the applied film. Unless the two adherend surfaces
are brought together at the right time between application and setting, a satisfactory
bond will not be achieved.
Wet tack
The wet tack refers to the initial cohesive strength of the adhesive film before solidifica-
tion. The tack must be great enough to hold the two adherend surfaces together after
they have been pressed into contact, even though the adhesive may be far from set.
Indeed, the wet tack actually relates to the green strength of the bond, that is its strength
before it has fully solidified.
Compression
After the two substrates have been brought together, compression of the joint is neces-
sary to bring all surfaces into close molecular contact. If one or more surfaces is porous,
increasing the compression increases the solidification rate. For example, with water-
based dispersions the rate of development of bond strength is a function of increasing
pressure because the low viscosity water phase is more rapidly dissipated into the
porous substrate by accelerated capillary action into the voids created by the tubular
cellulose fibres.
Solidification
The strength of the final bond is optimized when solidification is complete. The solidifi-
cation mechanism depends upon the type and composition of the adhesive. Generally,
solidification is initiated, progressed or accelerated by the application of one or more of
the following: high velocity warm air, infrared, heated platens, radio frequency heating,
ultraviolet light and electron beam curing.
Types of adhesive
Adhesives may be grouped by the process of bond formation during the solidification
phase. There are only three processes by which solidification may occur — drying, hot-
melt and curing — but there are many combinations of these bond-forming mechanisms.
Drying adhesives
In this type the adhesive polymer is dispersed or dissolved in a liquid carrier that may be
water or an organic solvent. The liquid phase is subsequently absorbed or evaporated in
order to create a solid bond; the adhesive dries by loss of carrier. It may be necessary to
apply heat energy to complete the drying process.
Solvent-based adhesives
Solvent based adhesives comprise polymers or elastomers (synthetic rubbers) dissolved
in an organic solvent. As the molecular mass of the polymer is increased so is its viscosity
but its wetting properties are successively diminished. During the drying process the sol-
vent evaporates and the solution thickens, eventually turning solid. The properties of the
final bond material are the same as those of the original undissolved substance and appli-
cation of fresh solvent will resolubilize the bond.
Water-based adhesives
In water-based adhesives minute particles of polymer or elastomer are suspended in
water to give emulsions (or more accurately dispersions). The viscosity of the emulsion
varies with solid content and is also a function of particle size. As well as emulsions,
water-based adhesives may take the form of solutions of polymers such as casein or poly-
vinyl alcohol. During the drying process water evaporates or is absorbed, the elastomer
particles are drawn together as the viscosity increases, and by strong mutual attraction
fuse into a solid film. Unlike solvent-based adhesives, emulsion materials will not redis-
solve because they were not soluble to start with.
Most thermoplastics (with the exceptions of polytetrafluoroethane, polypropylene
and most polyurethanes) can be dissolved in solvents; also, most rubbers with the excep-
tions of ‘viton’ and EPDM. The solid content of water-dispersed adhesives can be made
substantially higher than for solvent-based adhesives, which enables them to set faster.
A requirement for the successful use of drying adhesives is that at least one adherend
must be permeable to the carrier. The rate of liquid absorption is a function of viscosity
and molecular attraction (surface energies) but the structure of the porous substrate is
also very important. Rate-controlling factors include the density and geometry of cellu-
lose fibres, the nature of the clay coatings, the nature and extent of resin impregnation
and the presence of moisture-repelling materials in the substrate. In a way analogous to
problems experienced with printing inks (powdering) substrate coatings can also cause
difficulties for aqueous drying adhesives. For example, when aqueous dispersions are
used with carton board substrates finished with clay coatings, water may be absorbed
through the coating, leaving polymer particles on the surface. Although the polymer may
be strongly bonded to the coating, water penetrating it will soften the coating binder,
allowing the coating to detach when stressed.
Pressure-sensitive adhesives
Pressure-sensitive adhesives (PSAs) belong to the group of drying adhesives. However,
their mode of use is such that most of the drying takes place before the adherends are
joined together; pressure is required to optimize contact. They are generally used as
pressure-sensitive coatings for tapes and labels. They are based on soft polymers or elas-
tomers having long tacky intervals before final drying takes place. Because their tacki-
ness is long lived, labels and envelopes employing them have peelable or resealable
qualities. Both solvent and water-based types are used. In fact they are highly viscous liq-
uids that flow very slowly into the surface troughs of the adherend surfaces. In practice
they rarely harden once adhesion is complete and the material is unchanged from its
original state.
Hot melt adhesives
In this class of adhesives the bond is formed by solidification of molten adhesive by the
loss of heat. They are based on resins, waxes and thermoplastics which melt in the tem-
perature range 100–250°C. Current developments are aimed at reducing the softening
temperature and with it the dangers of cross-linking or oxidation of the adhesive. For-
mulations have become complex, resulting in hot melts that can give almost instanta-
neous adhesion to almost any substrate. Indeed, high-speed bonding to impervious
flexible packaging substrates hitherto not possible can now be achieved.
Hot melt adhesives must flow, wet both substrates and then cool rapidly to form a
strong adhesive bond. The final bond strength is attained when when the temperature
falls to that of ambient conditions. The viscosity must be low at the application tempera-
ture but not so low that excessive spreading and penetration occurs because this would
encourage blocking. (The same analogous term is used in printing to describe the stick-
ing together of printed paper in the reel by unset ink.)
The hot melt viscosity should remain low until the substrates are compressed
together. It should then rise rapidly with cooling, with a corresponding increase in cohe-
sive strength within the bond.
Hot melts generally consist of 100% solids thermoplastic polymers mixed with tacki-
fying resins and waxes. The largest group of hot melts is based on ethylene–vinyl acetate
copolymers (EVAs); polyamides and polyesters are also used. They are widely used in
high-speed packaging operations; as one-shot (flexible perfect binding) adhesives for
pocket books and magazines; in multishot applications for catalogues and in burst bind-
ing of books. (In burst binding the backbone of the book is burst or perforated to
increase the surface area of adhesion. In perfect binding the backbones of the signatures
are first cut off.)
Hot melts have many advantages over other classes of adhesives. They enjoy
extremely high tack, are very fast setting, giving production speeds that are both
high and economic. Since they are thermoplastic and reversible, overnight cleaning
of equipment is unnecessary. They do not require ancillary equipment such as UV or
EB curing to aid solidification, and therefore require less operating space with lower
capital overheads. Since they do not contain water or solvents which require heat
energy to dissipate them, operating energy costs are lower. Furthermore, organic sol-
vents that cause environmental concerns are excluded. Finally, if they are correctly
formulated they do not appear to have any age limit. Overall, although they are more
expensive than some other types of adhesives, it is considered that their higher cost is
offset by economies in operation.
The disadvantages are relatively few. They cannot be applied to surfaces that are sen-
sitive to and likely to be damaged by heat. Because they are thermoplastic the bond
formed is not heat resistant and will soften if the temperature rises to the glass transition
temperature (Tg). Conversely, the bonds may become brittle at low temperatures
although this can be offset by the addition of plasticizers.
Pressure-sensitive hot melts

Pressure-sensitive hot melts, based on thermoplastic rubbers, are finding favour as legis-
lations increase the environmental pressures to replace the VOCs used in conventional
solvent-based PSAs. Water-based dispersions require high energy consumption to dry
them and are also moisture sensitive. Moreover, wastewater from cleaning operations on
the coating line are classified as harmful waste products. The use of 100% solids systems
is therefore attractive. There are, however, limitations to thermoplastic pressure-sensitive
hot melts which include insufficient shear resistance at high temperatures, low chemical
resistance, degradation by ambient ultraviolet light and cold flow under pressure. A
recently introduced alternative is the UV curable PSA.
Applying hot melts

Figure 12.4 shows a schematic diagram for a hot melt roller application system in which
a hot melt reservoir supplies molten adhesive, at around 170°C, to the applicator roller.
Liquid adhesive at this temperature is applied to the first substrate which has an ambient
temperature of between 10°C and 20°C. Heat is transferred into the substrate as the liq-
uid flows and wets it, resulting in an initial temperature drop. This could be as great as
100°C by the time the web reaches the compression point where the second substrate is
pressed into contact. The tack and viscosity will by then have risen sharply, but the adhe-
sive is still essentially liquid because thermoplastic hot melts are amorphous in character
and therefore soften or harden over a wide temperature range.
Cycle: plus heat minus heat

Solid Liquid Solid
Open time
Adhesive film
First substrate
Good No bond
bond (A) (B)
Adhesive Compression
at 170°C point
Second
substrate
Figure 12.4: Hot melt roller application
At compression, where the second adherend (which is also at ambient temperature) is

pressed into contact with the film, further heat flow occurs into this substrate followed by
rapid cooling and bond formation. The temperature of the adhesive film at the point of
bond formation is called the bonding temperature. The rate of solidification, and
hence the rate at which the bond strength develops, depends upon the rate at which the
substrate can absorb heat from the melt. In turn, the thermal capacity and conductivity
of the substrate are the rate-determining factors for bond formation and these will vary
with substrate materials. A metallized flexible packaging substrate may well conduct heat
away faster than a fibrous mechanical paper containing insulating air voids or a paper
having a heavy mineral coating. Consequently, the same adhesive applied under the
same applicator conditions to different substrates having different thermal properties,
will have different open times. Therefore, as indicated in Figure 12.4, careful consider-
ation of open time must be given to deciding the compression point for the second
adherend. Too soon and the tack and viscosity may be too low, resulting in loss of adhe-
sive from the edges, and the possibility of blocking; too late and a bond is not formed.
Contact and compression over region A results in a good bond. Beyond A, in region
B, results in failure to bond.
Curing adhesives
The third and final class of adhesives is that in which solidification occurs as a result of a
chemical reaction, leading to curing. The chemical change may be brought about by
mixing two or more components, heating, or altering the conditions of the environment,
such as by interaction with moisture, oxygen or ultraviolet light. The chemical bonds
produced have such extremely high strength that there is little point in using them in
packaging applications where the substrates themselves are relatively weak. The excep-
tions are where the bonding of high-performance flexible packaging laminates are
required. Reactive hot melts are used for unsewn binding on difficult papers that would
normally have required sewing. The reactive adhesives can be further grouped into sub-
categories depending on their mode of application and curing.
Cure by mixing two or more components

Typically these are two-part epoxides that harden at room temperature. The more slowly
they cure, the stronger is the bond. These systems are used to bond materials such as
metals, plastics and ceramics where great strength is required. They are used in glass
fibre laminates, epoxide fillers and household adhesives such as Araldyte.
Cure when heated

These are solutions or dispersions that are activated by heat after they have wetted the
adherend surface. They are used in fast vacuum laminates and the successive bonding of
materials using preapplied adhesives. These adhesives may not fill out the joint and, for
successful bonding, one adherend must be able to match the contour of the other.
Exposure to moisture
Isocyanates react with hydroxyl groups such as those found in water. Thus polyure-
thanes, which contain isocyanate groups, will cure in the presence of water. In use, the
dry solid adhesive is applied to the adherend and subsequently moisture from the air or
substrate reacts with the isocyanate groups to give cross-linking. Although they cannot
be water based they can be formulated as either solvent-based or hot melt adhesives.
Preference is shown for the hot melt type because it eliminates the need for harmful
VOCs and the cross-linking overcomes the disadvantage of poor heat resistance found
with conventional hot melts.
Reactive hot melts are used for unsewn binding of difficult papers that would nor-
mally have been sewn. In packaging they are used for more demanding applications such
as hot filling, boil-in-the-bag and ovenable laminates. They also have high chemical resis-
tance for special applications.
Radiation curing
Both ultraviolet (UV) radiation and electron beam (EB) may be used to cure adhesives.
Electron beam radiation has energies that are thousands of times greater than the ener-
gies required to break chemical bonds and an initiator is not required. EB radiation is
absorbed by all matter regardless of its molecular structure, the depth of penetration
being a function of electron energy and material density. (The term ‘radiation’ should not
confuse EB with electromagnetic radiation. It is in fact a stream of high-velocity elec-
trons, but remember that these exhibit a wave function of their own (Chapter 1). Also,
when high-energy electrons strike a solid target such as a metal, their absorbed energy
may be converted to electromagnetic radiation in the form of X-rays.) A high-energy pri-
mary electron, in collision with an adhesive molecule transfers its energy to molecular
electrons, displacing them to give a cascade of secondary and tertiary electrons; these
create reactive groups randomly at polymer and monomer sites. The result is a high
degree of cross-linking in polymer systems without the need for photoinitiators.
In the case of UV radiation the photon energy is only comparable to the bond energies
in polymers. It is therefore necessary to initiate photopolymerization with the aid of a
photoinitiator that can absorb the photon energy and create free radicals which then
react with the monomer or polymer system. Thus, the polymer itself may be transparent
to the UV radiation which is then solely absorbed by the photoinitiator. Acrylate-based
adhesives have been developed for print conversion applications that dry by UV curing
of free radical systems. The chemistry is the same as for inks.
Radiation curing adhesives require high final molecular weights to give strength to the
final bond but low initial viscosity to promote good adhesion. These are achieved by
choosing a suitable blend of reactive diluents and prepolymers.
The advantages are that the adhesive can be applied as a low-molecular-weight liquid
with high wetting and adhesion properties, but which cure to give a high-molecular-
weight, strong bond. Since the curing is instantaneous, adhesive applicator machinery
can be run at fast speeds with low energy costs. The main disadvantage is that the adhe-
sive costs are comparatively high. However, higher machine speeds, the absence of sol-
vents and the extraction systems needed to remove them, means that overall the process
should be cheaper than conventional gluing.
There are certain restrictions, however. As with inks, high energy surfaces such as
PVdC films will be wetted by the highly polar UV polymer and monomer vehicle sys-
tems, but these will not adhere to low energy surfaces such as polyethylene, without sur-
face oxidizing treatments such as flaming or corona discharge. Second, by virtue of the
nature of application, at least one of the substrates being bonded must be transparent to
UV radiation (Figure 12.5). During application of the adhesive, the first substrate to
which it is applied must be nonporous to prevent absorption before the second substrate
is applied.
Adhesion to difficult substrates, such as polystyrene, polypropylene and polyethylene,
is achieved by using low shrinkage monomers such as dipropyleneglycol diacrylate
(DPGDA) although this has poor flexibility. Alternative formulations use prepolymers
having good adhesion properties coupled with multifunctional monomers. For example,
urethaneacrylate (prepolymer) together with tris(2-hydroxyethyl)isocyanate triacrylate
(THEICTA).
Ultraviolet curing pressure-sensitive adhesives
Radiation curing of pressure-sensitive adhesives has been applied to those coated from
solution and from aqueous dispersions, those polymerized from liquid monomer diluted
Collection reel
Substrate B
UV
radiation
Applicator
Substrate A
Figure 12.5: Application of UV curing adhesives
systems, and hot melts. The advantages of radiation-cured hot melts is that they over-
come the limitations of conventional hot melts, notably their heat sensitivity.
Although EB curing PSAs have been around for many years, UV curing systems have
only become a reality since the late 1980s. The first systems used cross-linking acrylates
containing initiators. Since they were oxygen sensitive, the adhesive was protected by
using a PET web liner. (Interference from atmospheric oxygen causes undercuring of
the film through two possible mechanisms: (a) quenching of the photoactivated initiator
in its excited triplet state, resulting in deactivation to the ground state; (b) scavenging of
radicals by oxygen to form stable peroxides. Oxygen can be excluded either by blanket-
ing with nitrogen gas, which is inconvenient, or by irradiating through a thin (36µm)
film of polyester (PET).
These UV free radical curing adhesives are used for tapes and, since no post UV reac-
tion of the soft elastomers occurs, the degree of cure is constant over long storage times.
A PSA tape can be produced by coating a web with the appropriate monomer mixture,
at ambient temperature, and then irradiating to give the desired degree of polymerization
of the elastomer.
A problem with using room temperature liquid monomer systems is the high degree
of unreacted residual monomer which renders them unsuitable for food packaging. Hot
melt UV curable PSAs have the advantage that, because they are solid to start with,
high-molecular-mass components that are not mobile and will therefore not migrate
from the joint into the packages contents, may be used. They are therefore useful for
applications where they are likely to come into contact with food.
The efficiency of the earlier UV curing PSAs was increased by combining the added
photoinitiator with urethane–acrylates and difunctional methacrylates. Further
improvements have been effected by copolymerizing the photoinitiator into acrylic
adhesives, an example being benzoin acrylate. The photoexcited initiator splits into a
radical at the polymer that can generate a second radical. Cross-linking occurs by the
combination of two polymeric radicals. These systems are not much affected by oxygen
and the hazard of free, unused initiator is eliminated. Improved adhesive performance
and cross-linking efficiency for acrylic adhesives is obtained using comonomer acryl-
ated resins as tackifiers.
These new polyacrylate adhesives using copolymerizable photoinitiators are consid-
ered to be safe for food packaging applications. Moreover, because the free radical reac-
tion takes place through copolymerized photoinitiators, double-bonded molecules that
would be susceptible to oxygen ingression need not be used. The absence of double
bonds also removes the possibility of thermal polymerization so that these materials are
suitable for hot melt PSAs that are chemically stable when heated. The basic components
of acrylic pressure-sensitive adhesives are soft acrylic acid–ester copolymers having low
glass transition temperatures.
Radiation curable hot melt PSAs are now available, that have postcure heat-
softening properties in excess of 180°C; traditional hot melts soften at 80–90°C.
Label adhesives that are used in laser or thermal transfer printers will be exposed to
temperatures of up to 200°C, which would soften conventional hot melts with subse-
quent damage to the printer.
Styrenic block copolymers
Styrenic block copolymers (SBCs) are now widely used in pressure-sensitive adhesives.
Although UV curing versions of these have now been developed, their noncuring coun-
terparts are widespread and these will be discussed first. The term ‘block’ refers to the
composition of the polymer which usually comprises three components arranged in a
sequence A–B–A. Moreover, they can be designed to be UV curable.
In styrenic block copolymers an elastomeric mid-block is attached at either end to a
thermoplastic styrene end block. The elastomeric mid-block may be a rubber such as
polybutadiene (the SBS block copolymer series), polyisoprene (the SIS series), polyeth-
ylene/butylene copolymer (the SEBS series), or polyethylene/propylene copolymer (the
SEPS series). These materials are called thermoplastic elastomers because they com-
bine the properties of both elastomers and thermoplastics. The structures are shown in
Figure 12.6.
Elastomer
Styrene Styrene
mid-block
n m n
(a)
[ CH2 CH CH CH2 ]m
polybutadiene SBS block copolymer
CH3
CH2
[ (CH2 CH2)x (CH2 CH)y ]m

polyethylene–butylene SEBS block copolymer
CH3
[ CH2 CH C CH2 ]m
polyisoprene SIS block copolymer
CH3
[ (CH2 CH2)x (CH2 CH)y ]m

polyethylene–polypropylene SEP block copolymer
(b)
Figure 12.6: Styrenic block copolymers: (a) general structure; (b) types of elastomer mid-blocks
In conventional noncuring hot melt or solvent-based block copolymers the styrenic

end groups interlock or cross-link in physical three-dimensional networks as indicated
in Figure 12.7. Above the glass transition temperature of polystyrene it starts to soften,
the physical interlocking cohesive forces are overcome and the polymer flows. When
the melt is cooled down once more, the styrenic end blocks resolidify and the polymer
regains its original strength. The mid-block elastomer provides the pressure sensitivity
of the adhesive.
Although there are many PSA applications for these materials, they will not withstand
solvents or temperatures above the Tg for the thermoplastic styrenic end groups. Radia-
tion curing overcomes these problems.
Styrenic end groups
Elastomer mid-block
Figure 12.7: The morphology of a styrenic block copolymer. The thermoplastic styrenic end
groups freeze to give reversible physical cross-linking
Ultraviolet curing SBCs

As with other UV curable systems, a photoinitiator must be included to produce free
radicals which then promote cross-linking. In block copolymers the physical cross-linking
of the styrenic end blocks may be reinforced by cross-linking across molecules of the
elastomeric mid-block. For this to occur, the elastomeric mid-block must contain unsat-
urated double bonds with which the free radicals created by the excited photoinitiator
can react. Suitable mid-block elastomers are therefore polybutadiene and polyisopro-
pene. The first radiation curable styrenic block copolymer was based on polyisopropene
and employed benzyldimethylketal (Irgacure 651) as the photoinitiator.
Comparison of the stages involved in bond formation
Figure 12.8 shows the time taken to form a bond strong enough to withstand shearing
forces within the adhesive film but breaking instead in the body of the fibre board. The
adhesives compared are a solution adhesive of 45% solids dextrin, an emulsion adhesive
comprising 45% solids polyvinyl acetate, and a hot melt comprising 100% solids. The
application viscosities of all three were similar and they were applied to board.
The solution (dextrin) adhesive bonds primarily by mechanical adhesion. The rate of
bond formation depends on how quickly water is lost into the board. The adhesive film
100% Fibre tear
Hot melt 45% solids 45% solids

PVA Dextrine
Bond strength
0 10 20 30 40
Time (s)
Figure 12.8: The time taken to form a 100% fibre tearing bond for hot melt, emulsion and
solution adhesives
Source: Pira Teach-in T3 An Introduction to Adhesives 1982
does not begin to develop useful tack and strength until the solids content between the
surfaces is greater than 95%. At this stage the bond is strong enough to exhibit 100%
fibre tear when the surfaces are pulled apart. The time for this to occur approaches 40s.
The emulsion polymer is a stabilized suspension of polymer particles in water held
apart by repulsive forces. The primary drying mechanism is again absorption of water
into the substrate but now causing the polymer particles to draw together and coalesce.
Coalescence into a continuous film occurs when the solids content has risen to only
70%, that is when there is still about 30% water left in the film. At this point the film has
sufficient strength and tack to exhibit 100% fibre tear. The full bond strength is attained
when the remaining 30% of water absorbs into the substrate and subsequently into the
atmosphere. The bond strength reaches 100% when all the water has evaporated. The
bond strength of the emulsion adhesive reaches that of the dextrin solution in about half
the time, which is why these adhesives have replaced dextrin-based solutions for many
packaging applications.
The hot melt adhesive shows the fastest bond formation of all three, reaching 100%
fibre tear in only 4s. The reason is that there is no solvent carrier to be absorbed into the
substrate and subsequently lost in the atmosphere.
The processes by which adhesives solidify may be summarized as shown in Figure 12.9.
Adhesive classes and properties
Acrylics
Polymers and copolymers based on acrylates, methacrylates and other comonomers are
used in the form of emulsions and solutions. Adherends to which they are suited include
Curing
Drying Cooling
(polymerization)
Solvent or water Mixing of two Hot metal

evaporates components adhesives
70–80% of the hardens at room hot adhesive
adhesive is solvent, temperature — faster solidifies on cold
or 50% if water; when heated surface
evaporation causes
adhesive to shrink
Heating of single Adhesive films
component melt between
Joint drying temperature 100°C adherend surfaces
at least one or more
adherend must be
permeable to liquid Heat activated
carrier Changing the applied to surfaces
environment and dries to form a
contact with film which is
Pressure-sensitive moisture exposure; activated using heat
adhesives to UV; change
most of the drying of pH
takes place before
the materials are
joined together
Tape form
the material in the
board line and on
the roll have the
same properties
Figure 12.9: The hardening processes for different classes of adhesives
paper, coated boards, aluminium, plastics, wood and textiles. Their applications are
many fold and include pressure-sensitive and heat seal coatings. Pressure-sensitive coat-
ings used for tapes and labels employ very soft, tacky polymers as water-based or
solvent-based acrylics. Water-based dispersions are used for general-purpose labels.
Solvent-based acrylics are used for more demanding applications such as peelable or
deep-freeze labels.
Heat seal acrylates are used for lidding. These are hard, tack free polymers that can be
formulated to bond many plastics and aluminum foil and can heat seal at relatively low
temperatures. They may be applied in both water or solvent based forms.
Animal glues
These consist of mixtures of gelatins extracted from animal hides and bones. They are
available as slab jelly or hard granules and are generally used in solution in water — more
correctly described as a colloidal sol. They are suitable for gluing paper, wood and tex-
tiles. Animal glues offer an aggressive tack with a medium setting speed and are used for
case making and lining, and occasionally in unsewn binding lines. Their use in packaging
is now restricted to applications that require high tack such as cardboard box making,
file making and abrasive paper manufacture. Their disadvantages are that they age under
dry warm conditions such as is provided by central heating, becoming brittle and crack-
ing. Moreover, their biodegradation stability is poor.
Casein
Casein is the protein component of milk which is solubilized by treating with aqueous
alkali. Starch may be added to increase its viscosity and tack. Suitable adherends are
paper, glass, tin plate, wood and textiles and it consequently finds application in the
packaging industry for labelling glass jars, bottles and tins. It is often incorporated into
rubber latex adhesives to increase their heat and creep resistance. As a single-component
adhesive, it suffers biodegradation, being susceptible to attack by microorganisms.
Starch
Starch is used as an adhesive in its unmodified as well as in several modified forms.

Starch, (C6H10O5)n is a polysaccharide, which is a high polymer of the polymeric sug-
ars and related to cellulose (C6H10O5)n, the major constituent of paper. It occurs in all
green plants but the commercial sources are maize, wheat, barley, rice, potatoes and
tapioca. For adhesives, maize, potatoes and wheat are of most importance. The plant
cells are broken down by grinding and washing with water, and the starch granules
sieved and dried.
Starch is not soluble in water and as an untreated slurry has no adhesive qualities. In
order to produce the required adhesive properties the starch granules must be heated
with water which they absorb and then burst to give a gelatinized paste having an open
tacky formation. Simple pastes produced in this way have very high viscosities at low sol-
ids contents which produces weak bonds. They are therefore no longer used in this sim-
ple form. The solids content is raised and the viscosity lowered by combining the high
viscosity paste with a low viscosity, unheated slurry of starch granules. An alternative
formulation partly converts the starch granules by heating to give an intermediate viscos-
ity and higher solids content. Because each of these formulations contains ungelatinized
starch granules, heating of the green bond is necessary after application. These starch
pastes have low wet tack and setting speeds and are suitable for paper, wood and textile
adherends. Their adhesion is greatest with paper because they share a family affinity with
cellulose but they are softened by water and attacked by microorganisms. The most
important use of unmodified starches is in corrugated board production where their
advantages of good adhesion, low cost and ease of recycling are favoured (they disperse
rather than produce stickies). Their main disadvantage is that they must be heated to
complete gelatinization which limits their use to small numbers of board plies because
heat cannot penetrate multiwall boards effectively enough. More expensive cold set
adhesives such as polyvinyl acetate must be used for multiwall board production.
Dextrins
Starches can be modified by various thermal and chemical treatments. The dextrins are
produced through partial hydrolysis of starch by boiling with water under pressure at
250°C. They produce white powders which, depending on the degree of hydrolysis, may
yield either pastes or clear solutions with water. The adhesive preparations are classified
as glues when they are liquid and gums when they are pastes. As well as adhesives, they
are also used in the preparation of paper sizes (and in confectionery). Suitable adher-
ends are paper, glass and textiles.
Applications in bookbinding include end papering (the first and last leaves of a book),
tipping (gluing in a separate sheet), and leather hand casemaking. In packaging the high-
tack low-water-content gums are used in bottle labelling, whereas the glues are used in
case sealing and tube winding. In common with all starch-based adhesives, the dextrins
have poor biodegradation resistance because their relationship with the saccharides (sug-
ars) makes them attractive to microorganisms. The problem can be reduced in all starch-
based preparations by the inclusion of biocides.
Other modified starches may be prepared by varying the combination of mechanical,

thermal and chemical treatments to give a range of adhesives having quite different
properties and applications. Their uses range from labelling glass bottles and jars, where
a high-viscosity high-wet-tack gel is necessary to enable successful high speed transfer of
the label, to the highly pasty absorbent-resistant adhesives required in the manufacture
of porous paper bags.
Pregelatinized starch
Pregelatinized starch is produced as a result of gelatinizing the starch granules by heating

them with water and then rapidly drying the slurry. The process imparts the advantages
of full gelatinization while maintaining a relatively high solids content and workable vis-
cosity. It is soluble in cold water, shows high adhesion to paper, wood and textiles, and
can absorb quite large volumes of water without losing its paste characteristics. It there-
fore finds useful application in the manufacture of paper sacks where two adhesives are
required, a low viscosity type for gluing the edges of the continuous tube of paper, and a
very pasty one for for sealing the ends of the sack. The main disadvantage of pregelati-
nized starch is its slow drying.
Ethylene–vinyl acetate copolymer hot melts
Most hot melts are based on ethylene–vinyl acetate (EVA) copolymers which act as
binders and give the adhesion properties, resins to improve tack and wetting, and waxes
to reduce the melt viscosity. The number of formulations is extensive in order to meet
the range of applications in packaging and bookbinding operations. There are three
ranges of application temperatures: 100–120°C, 140–160°C and 160–180°C, with soft-
ening points lying between 65° and 110°C, depending on the resin components. The
lower application ranges are suited to uses where thermal stability to higher product
resistant temperatures is not important. They have the small advantage of some energy
savings in running the applicator at lower temperatures.
Conventional hot melts are widely used in many high speed packaging operations.
An interesting application is in the production of wrap around case sealings, an opera-
tion in which a case is constructed around the items to be packed in a single stage. All
the seams are joined at the same time by the application of the hot melt through jets. In
print finishing operations they are used in the high speed production of magazine and
catalogue bindings. Suitable adherend substrates include paper, coated or varnished
boards, plastics, wood and textiles. EVA hot melts suffer from low heat stability and
poor solvent resistance.
Polyamide hot melts
Polyamide hot melts are based on thermoplastic polyamide resins. Although they
offer better solvent resistance than EVA, they are difficult to use because they oxidize
when hot in the presence of air. For this reason they are usually avoided if EVA can
possibly be used. However, they are suited to paper, aluminium, plastics, wood and
textile adherends.
Polyester hot melts
Polyester hot melts are also thermoplastics but demonstrate an exceptional heat
resistance not found with other heat reversible polymers. The high thermoplastic
heat stability is a result of a high transition glass temperature. Consequently, they
have the inherent disadvantage of high application temperatures. Also, the melting
range is quite sharp which means that the open time is short, leaving little room for
error in the operating conditions. They are therefore only used where high heat resis-
tance is required and where UV curing lines are not available. However, suitable adhe-
sives include paper, aluminium and textiles.
Rosin hot melts
Natural resin or rosin is obtained from pine trees and was the first hot melt to be used
by mankind. Although still in use as a single component, it may also be formulated with
ethylenevinyl acetate copolymer to increase cohesion of the melt. Suitable adherends are
paper, tinplate and glass. Applications include jar and can labelling by applying two
blobs of rosin which enables the can to pick up and position the label. The edges of the
label are applied with a starch paste which gives all round fixing. Rosin hot melts are
cheap but have high tack and adhesion towards glass and tin. Although the rosin is brittle
when solid, the starch adhesive ensures tenacity of the label.
Natural rubber–latex adhesives
These elastomers have the ability to form nontacky films which bond on contact. They
therefore belong to the family of pressure-sensitive adhesives (PSAs). Suitable adher-
ends are paper and cellulose films. In applications such as instant seal envelopes, the
latex is modified to give a balance of adequate adhesion with the substrate coupled with
cohesion within the elastomer. When two coated surfaces are brought into contact, high
cohesion holds them together. By engineering the strength of the cohesive forces, the
product can be made permanent or peelable and resealable. Natural rubber latices are
also used in the preparation of cold seal adhesives — by formulating with acrylic res-
ins, the bond is formed by applying pressure. These cold seal adhesives find applications
in packaging, where heat-sensitive foods such as biscuits and chocolate are wrapped in
cellulose films.
Polyurethanes
The polyurethanes provide a wide range of adhesives which may be solvent based, water
based or hot melt. Furthermore, within these classifications they may be thermoplastic or
reactive, either as one-component or two-component systems.
The reason for their versatility and diversity lies in the chemistry of the urethane
groups. These are formed by the reaction of isocyanates with hydroxy groups, and in this
respect there are very many possible combinations involving a variety of polyisocyanates
and hydroxy-group-containing polyols such as polyesters and polyethers (Chapter 5).
The cross-linking varieties cure by one of three mechanisms:
● In two-component systems, isocyanate and polyol react when brought together

in a mix. These can be solvent based or mixed in their undiluted states, but they
have the disadvantage of a limited pot life.
● In one-component systems, mutually reactive polyisocyanate and polyols are

premixed, but the reactive isocyanate group is prevented from making contact
with the reactive hydroxy groups in the polyol until the adhesive is required to
function. This is achieved by temporarily isolating the isocyanate group by
loosely attaching another but unreactive chemical group. When heated this
group detaches, leaving the polyisocyanate free to react with the polyol. This
variety may be 100% solids, solvent or water-based dispersions and solutions.
● Since the isocyanate group reacts with hydroxy groups, the polyisocyanates can
be made to react with water to give moisture curing adhesives. These are dry
adhesives applied in the absence of moisture but which cross-link in the
presence of atmospheric or paperborne moisture.
The diversity of varieties of polyurethanes goes together with the diversity of applica-
tions. Overall they exhibit very good adhesion qualities with a large range of packaging
films and papers. They have extremely good heat, cold, solvent, oil and biodegradation
resistance, which makes them very popular in packaging applications, for example in
the laminating of flexible packaging films. These flexible laminates are used in a range
of packaging applications where heat resistance is required, such as boil in the bag and
ovenable products. They are also used in some book-finishing applications such as dif-
ficult unsewn bindings.
Polyvinyl acetate (PVA)
Although hard and brittle, PVA is a thermoplastic and can be made more flexible by the
addition of plasticizers. PVA dispersions in water form the white glues used in the
unsewn or perfect binding of pads and paperback books. They are also used for end
papers (the first and last leaves of the book), for tipping (gluing in a separate sheet), glu-
ing off (reinforcing sections), casing in (inserting the book into the case), spine gluing
and side gluing. They are widely used as primers for certain hot melts on unsewn bind-
ings. In packaging they are used on most substrates involving paper, board and some
plastics (with the exceptions of polyvinyl chloride, polyethylene and polypropylene).
Examples are cold set corrugating, lap glues, case sealing, carton forming, carton sealing
and tube winding. Adherends include paper, coated boards (not all), plastic films (not
all) polystyrene, wood and textiles.
Overall, PVA is an important and versatile adhesive which is cheap, fast setting and
able to cope with changes in the quality of the substrate offered. Disadvantages include
only moderate water and poor heat resistance. Also, the plasticizer tends to weaken the
polymer or else migrate, thus reducing its flexibility.
Polyvinyl alcohol
Polyvinyl alcohol is water soluble and is used as a solution in which mineral fillers may be
dispersed if it is necessary to increase the solids content. Fully hydrolysed polyvinyl alco-
hol gives films that are quite water resistant. If only partially hydrolysed, the films are
sensitive to water. The adhesive is suited to paper and textile adherends.
Polyvinyl alcohol yields solutions having high viscosity and tack with low solids con-
tent, and its low cost makes it popular for high volume paper conversion applications
such as board lamination, tube winding and wallpaper duplexing. Fully hydrolysed poly-
vinyl alcohol is used where water resistance is important. The partially hydrolysed form
is useful where remoistenable films are required; for example postage stamps.
Polyvinylidene chloride
Polyvinylidene chloride has relatively poor adhesive qualities but offers extremely good
barrier resistance towards water vapour and gases. It is therefore used as an adhesive
for flexible packaging, for example aseptic packaging, where barrier requirements are
important.
SBS and SIS block copolymers
Styrene–butadiene and styrene–isoprene block copolymers have rubber-like properties

at room temperature due to their elastomer mid-blocks. They soften on heating when the
styrenic end blocks are loosened from their physical cross-linking structure. They are
used in pressure-sensitive hot melts, having suitability for adherends including paper,
glass, plastics, wood and textiles.
Because of their high cohesive strength and creep-resistant properties they perform
better than ethylene–vinyl acetate copolymers in label and tape applications.
Styrene–butadiene rubber
The styrene–butadiene copolymer elastomer formulated with tackifying resins can be

prepared as either a solvent or water-based pressure-sensitive adhesive. It is used in
pressure-sensitive tapes and labels and also laminations. Its poor creep resistance is
improved for laminating applications by formulating with casein.
Vinyl acetate copolymers
Vinyl acetate copolymers other than those with ethene (ethylene) include acrylates and
maleates. They have in common with EVAs the properties of adhesion to plastics but can
be formulated to give soft films having long open times.
Vinyl acetate–ethylene copolymers for liquid applications
The application of EVA copolymers as hot melts has already been discussed. The
amount of ethene incorporated into the copolymer influences the degree of cross-linking
that can occur and a range of materials extending from the hard and tough to the soft
and tacky can be formulated. They are used as water-based dispersions which are white
in appearance and have a high solids content.
These have become very important adhesives because they can be applied to a wide
range of substrates, including paper, coated or varnished boards, polymer films, alumin-
ium, wood and textiles. Low energy surfaces such as polypropylene film can be lami-
nated and carton materials can be varnished all over before gluing rather than spot
varnishing. Plastic bottles can be wet labelled cheaply and, overall, this class of adhesives
offers lower cost alternatives to more expensive materials such as PSAs.
Theories of adhesion
Since even optically flat surfaces are comparatively rough on a molecular scale (40nm at
best), two surfaces brought together are rarely in contact over more than 10% of their
common areas. The first function of an adhesive is to make contact with and wet both
surfaces, bonding the high points but also filling the troughs to give a bond of uniform
strength (Figure 12.1). The strength of the bond then depends upon that of the glue line
between the two surfaces (cohesive) and the adhesive forces between the adhesive and the
substrate. The primary function of an adhesive is to provide a mechanical continuum
from one phase to another.
There are two main theories that attempt to explain the principles of adhesion. These
are mechanical (physical) adhesion and chemical adhesion. Bonds formed with paper
and board products employ both mechanical and chemical types of adhesion. There
have been a number of theories which attempt to explain chemical adhesion and these
include adsorption (1935), electrostatic (1950), diffusion (1960), molecular dispersion

(1951), chemical reaction (1960), and thermodynamic adsorption (1963). Only the
most popular of these will be discussed.
Mechanical adhesion
Mechanical adhesion only operates with absorbent materials. The polymeric adhesive
molecules penetrate the crevices of the adherend surfaces, and interlock with both them-
selves (cohesion) and the solid surface (adhesion). The mechanism has been likened to
the formation of a haystack which owes its structure to the intermingling of the long
grass stalks. These mechanical forces are relatively weak and depend upon the degree of
physical intermingling. If the lengths of the fibres are reduced they can pack more effi-
ciently and the resulting physical forces holding them together increase.
The analogy is drawn with polymer chains intertwining with the crevices of an adher-
end to produce a mechanical bond. Smaller polymer molecules can intermingle more effi-
ciently giving relatively high bond strengths. Mechanical adhesion is considered to be the
major contributor in the bonding of paper to paper and rubber to textiles. Mechanical
adhesion therefore will be assisted if the adhesive polymer is delivered into the substrate in
a carrier such as a solvent or water.
For example, water-based starch or dextrin emulsion adhesives readily bond paper to
paper because the water can quickly and easily wet the substrate, carrying with it the
adhesive. In the dried bond, the glue line between the surfaces is an homogeneous layer of
intermingled polymer molecules, whereas the regions just inside the substrates are a mix-
ture of intermingled chains and substrate fibres. Because the paper fibre polymer chains
are longer than those of the adhesive polymer, they are less strongly bonded together and
overstressing the bond will result in the substrate fibre chains failing before those of the
shorter polymeric adhesive.
Surprisingly at first sight, the expectation that substrates having the most open and
porous structures will form the strongest (mechanical) bonds is not fulfilled. Shear test
measurements have shown that it is the smoothest surfaces that give the strongest
bonds. Since the reverse would be expected if mechanical adhesion is the prime factor,
other forces must be taken into consideration. The role of chemical adhesion must
therefore be examined.
Chemical adhesion
The various theories that attempt to explain chemical adhesion rely on the surface mole-
cules at the adherend–adhesive interface approaching one another closely enough for
bonding forces to come into play. As neutral molecules approach one another, attractive
forces between them increase in a magnitude that depends upon the arrangements of
their outermost electrons. The physical forces of molecular attraction are known collec-
tively as van der Waals forces. In nonpolar species the electron clouds oscillate evenly
along the molecule and the associated attractive forces are called dispersion (London)
forces. In molecules containing polar groups the permanent dipole–dipole effect results
in additional attractive forces, the magnitude of which depend on the the electronegativ-
ity of the polarizing molecule. Electrons that are shared between molecules form strong
covalent bonds which are considered to be chemical rather than physical in nature. The
energy contents of these various kinds of bonds are given in Table 12.2.
As molecules approach one another even more closely, their associated negatively
charged electron clouds mutually repel one another, pushing the molecules apart.
There is therefore an equilibrium position where the attractive and repulsive forces are
balanced. Figure 12.10 indicates how these attractive and repulsive forces vary with
molecular separation. At separations greater than 0.5 nm, neither attractive or repulsive
Table 12.2: The energy contents of different bonds
Bond Energy (kJ mol–1)

Ionic bond 590–1050
Covalent bond 63–710
Metallic bond 113–347
Hydrogen bonding involving the F atom 0–42
Hydrogen bonding without the F atom (O, S etc.) 10–26
Other dipole–dipole (Cl, Br etc.) 4–20
Dipole–induced dipole 0–2
Dispersion (London) forces 0.08–42
forces are large enough to operate. As the separation becomes less than 0.5 nm, the
attractive forces increase and reach an optimum value, after which the forces of repul-
sion increase. It can be seen from Figure 12.10 that, for any one of the types of attrac-
tive forces depicted to become significant, molecules must approach one another
closer than 0.5nm. This explains why solid surfaces cannot be brought into close
enough contact for them to stick together naturally; the very smoothest have a 40 nm
profile. Further, it explains why an adhesive must wet the adherend surfaces. In so
doing its polymer molecules exercise the optimum closeness required to maximize the
attractive forces.
+160
+80 Dispersion forces

Increasing
repulsion
Energy (kJ mol–1)
0
0.1 0.2 0.3 0.4 0.5 Distance (nm)
Increasing
attraction
–80
Hydrogen bond
–160
Covalent
–240 bond
Figure 12.10: The variation of potential energy with distance for various types of bond
Theories of chemical adhesion
The main theories of chemical adhesion, i.e. those having the most evidence to support
them are: adsorption, a surface phenomenon whereby the adhesive is adsorbed onto
the adherend; diffusion, a volume phenomenon whereby the adhesive and adherend
diffuse into each other; and electrostatic, a surface phenomenon whereby the adhesive–
adherend system behaves as an electrical capacitor. An additional topic is chemical
reaction theory.
Chemical reaction thoery

The chemical reaction theory is short of supporting experimental evidence but there
are strong indications that it does occur in certain specific instances. The theory is that
adhesion takes place by the formation of primary bonds that result from specific pri-
mary valency bonds. Examples include the adhesion in glass fibre reinforcing, where
covalent primary bonds occur, and in welding and soldering where primary metallic
bonds are made.
Adsorption theory
This is the most widely accepted theory of adhesion and the adsorption processes are
considered to be the major factor in bonding; it has been developed by Zisman et al. in
the USA. The theory is based on the secondary forces that occur between molecules, that
is those of the van der Waals type. As described earlier, these are short range forces that
require mobile liquids and good wetting of the adherend, in order to bring molecules
close enough together. The adhesive strength increases with the strength of adsorption of
adhesive molecules onto the substrate. The important parameters in this theory relate to
wettability (and therefore to the surface energy of the solid), surface tension and viscous
behaviour of the liquid.
The formation of a bond by adsorption occurs though two different stages. In the first
stage, micro-Brownian motion takes place in the polar groups of the liquid adhesive.
This movement enables the polar groups to seek out their opposite counterparts in the
substrate groups. The application of mechanical pressure brings the surface active
groups sufficiently close together for them to interact. For this reason the application vis-
cosity must be suitably low. At the optimum close approach, van der Waals forces come
into play and adsorption occurs. (Figure 12. 11). The theory explains why impervious
substrates which are unable to support mechanical adhesion can be bonded.
+ – + – + – +
– + – + – + –
+ – + – + – +
– + – + – + –
+ – + – + – +
– + – + – + –
Figure 12.11: Representation of how polarized substrate and adhesive molecules are attracted
by van der Waals forces. In nonpolar molecules the oscillating electron clouds create molecules
whose ends change polarity at the frequency of oscillation
Electrostatic theory
The electrostatic theory proposed by Derjaguin has prominence in Russia. The adhesive
and adherends are considered to constitute an electrical capacitor in that the adhesive–
substrate interfaces have a charge separation across them. The double electric layer pro-
duced at the interface between the adherend and adhesive polymer molecules represent
the plates of a capacitor.
The theory concentrates on the forces that come into play when the bond fractures.
The pulling apart of an adhesive substrate interface is analogous to separating the plates
of a capacitor. An electric potential is established, the magnitude of which increases with
increasing surface separation, until an electrical discharge occurs, and the plates (sur-
faces) separate.
Although apparently mathematically sound, the theory is not fully supported by expe-
rience. For example, nonpolar materials do not have the permanent dipoles required to
satisfy the capacitative model, and yet they are able to exhibit good adhesion. Also, car-
bon black has been added to adhesive formulations, which greatly increase the electrical
conductivity of the adhesive and would not allow a capacitative device to hold its charge.
One would then expect very low bond strengths to occur and this is not found to be the
case. Observations such as these limit the reliability of the electrostatic theory in predict-
ing whether an adhesive will form a strong bond with a particular substrate material.
Diffusion theory
The diffusion theory is attributed to Voyutski and, unlike those discussed so far, is a vol-
ume phenomenon. The suggestion is that polymer adhesive molecules diffuse into the
substrate and lock mechanically into the surface structure, after which no clearly defined
interface exists. The theory only applies to high-molecular-mass materials and there is
some evidence that adhesives and substrates which are mutually soluble, operate this
mechanism. However, it is difficult to visualize the concept of polymer molecules diffus-
ing through hard, impenetrable surfaces.
In fact none of the foregoing theories completely explains the mechanisms of bonding,
when taken in isolation, but the adsorption theory is widely held to be the most useful.
Contact angle and wettability
The principle of contact angle measurement and its relationship to surface energy and
surface tension were discussed in Chapter 7. The mathematical relationships that enable
surface energy to be calculated from contact angle measurements are well established.
The contact angle is the angle made between a liquid (in this case the adhesive) and the
solid (adherend) interface. It is measured through the liquid to the tangent drawn to its
surface, as shown in Figure 12.12.
γ lv
Vapour Vapour
Liquid θ
γ sl γ sv
Solid Solid
Figure 12.12: Sessile drop profile and the relationship between the three interfacial tensions
(solid–liquid γsl; solid–vapour γsv; liquid–vapour γlv) and contact angle θ
Complete wetting of a surface will occur only when the contact angle is zero. In order
to anticipate whether successful adhesion is viable, it is necessary to be able to predict
whether wetting will occur for a particular solid surface and a given liquid (adhesive).
This prediction can be made through a knowledge of the critical surface tension of
wetting γc for the surface.
The critical surface tension of wetting for a particular surface is established by placing
different liquids on it and measuring their contact angles. These will vary depending
upon the relationships between the surface tension of the liquid and the surface energy
of the solid. A graph is plotted of the surface tensions of different liquids against the
cosine of the contact angle (cos θ) as shown in Figure 12.13. As the contact angle
decreases, cos θ tends to a value of 1. When the contact angle equals zero, complete wet-
ting occurs and cos θ = 1 (since mathematically cos 0 = 1). If the graphical plot obtained
in Figure 12.13 is extrapolated to cos θ = 1, the surface tension γc is the critical surface
tension of wetting for the solid. In practice it is only necessary to measure the surface
tension of enough different liquids to give a plot accurate enough to extrapolate to γc.
γc
1.0
0.8
0.6
Cos θ
0.4
0.2
0
0 10 20 30 40
Surface tension (mN m–1)
Figure 12.13: Plotting the cosines of the contact angles (cos θ) for different liquids having different
surface tensions, to establish the critical surface tension of wetting for a given solid surface
Once a solid surface has been characterized in this way it is only necessary to mea-
sure the surface tension of a particular adhesive in order to predict how well it will
wet the substrate. This is very useful in predicting the likely wetting of polymer films
by given adhesives.
In bonding systems using high polymer melts or epoxies, a low viscosity is also
required to ensure that flow is completed and the surface wetted before the melt sets.
Thus, in addition to approaching the critical surface tension of wetting for the adherend,
control of adhesive viscosity is also required. Hot melt polymers have to be able to with-
stand the high temperatures necessary to reduce the viscosity, without cross-linking or
degrading during application.
Surface modification
A further requirement for producing strong adhesive joints is that weak boundary layers
must not be present in the adherend surfaces as they will detach from the body of the
substrate, causing the joint to fail. In the case of polymers that may have mechanically
weak surface layers, surface treatment of the polymer may increase cohesive strength in
its surface regions. Surface treatments have long been used to increase the surface
energy of polymer films in order to improve their wetting properties. However, surface
strength may also need to be increased for the reasons given. Some polymers such as
nylons are relatively easy to wet (surface energy for nylon 6,6 is 43mNm–1) but are dif-
ficult to join adhesively, probably because they have mechanically weak surface layers.
Thus, although good wetting is essential, it is not enough on its own to ensure a strong
adhesive joint.
It is thought that the surface treatments used to improve adhesive bonding change the
surface region mechanically as well as in its wetting characteristics. For instance, corona
discharge treatment of the polyalkenes not only increases the critical surface tension of
wetting by introducing polar functionality into the surface, but also changes the constitu-
tion of the surface by chemical cross-linking, which in turn increases the cohesive
strength of the polymer surface. The mechanical strength of the surface regions is
thereby increased.
A number of surface treatment techniques have been developed with the aim of
cross-linking the surface regions and upgrading their mechanical strength without
changing the critical surface tension of wetting. The glow discharge treatment is one
such and is the basis of the CASING technique (Cross-linking by activated species of
inert gases). The substrate is bombarded with activated helium. When polythene is sub-
jected to this treatment, joint strengths are found to increase by a factor of 4–5. The
polythene surface has to be cross-linked to a depth of 50–100 nm to form a strong joint.
Glow discharge treatment of nylons has been found to increase their surface strength by
a factor of 3.
Metallized polymers that have good barrier properties are very popular in flexible
packaging operations today. The metal, such as aluminium, is vacuum evaporated onto
the surface of a plastic such as polythene with which it forms very strong adhesive joints.
Chemical analysis has shown that the process of metallization forms a cross-linked layer
in the surface regions of the polymer, forming a strong boundary layer and consequently
a strong joint.

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6330-12 Page 297 Wednesday, May 3, 2000 3:52 PM

298 Printing materials: science and technology

Polymers such as those used in flexible packaging present wettability problems

Adhesion and adhesives 299

Surface energy (mNm–1)

Table 12.1: Surface energies of polymer substrates

300 Printing materials: science and technology

Operating parameters for adhesives

Adhesion and adhesives 301

302 Printing materials: science and technology

Hot melt adhesives

Adhesion and adhesives 303

Pressure-sensitive hot melts

Applying hot melts

Cycle: plus heat minus heat

Figure 12.4: Hot melt roller application

At compression, where the second adherend (which is also at ambient temperature) is

304 Printing materials: science and technology

Cure by mixing two or more components

Cure when heated

Adhesion and adhesives 305

Ultraviolet curing pressure-sensitive adhesives

306 Printing materials: science and technology

Figure 12.5: Application of UV curing adhesives

Adhesion and adhesives 307

Styrenic block copolymers

[ (CH2 CH2)x (CH2 CH)y ]m

[ (CH2 CH2)x (CH2 CH)y ]m

308 Printing materials: science and technology

In conventional noncuring hot melt or solvent-based block copolymers the styrenic

Styrenic end groups

Ultraviolet curing SBCs

Comparison of the stages involved in bond formation

Adhesion and adhesives 309

100% Fibre tear

Hot melt 45% solids 45% solids

Adhesive classes and properties

310 Printing materials: science and technology

Solvent or water Mixing of two Hot metal

Figure 12.9: The hardening processes for different classes of adhesives

Adhesion and adhesives 311

Starch is used as an adhesive in its unmodified as well as in several modified forms.

312 Printing materials: science and technology

Other modified starches may be prepared by varying the combination of mechanical,

Pregelatinized starch is produced as a result of gelatinizing the starch granules by heating

Ethylene–vinyl acetate copolymer hot melts

Polyamide hot melts

Polyester hot melts

Adhesion and adhesives 313

Rosin hot melts

Natural rubber–latex adhesives

● In two-component systems, isocyanate and polyol react when brought together

● In one-component systems, mutually reactive polyisocyanate and polyols are

314 Printing materials: science and technology

Polyvinyl acetate (PVA)

Adhesion and adhesives 315

SBS and SIS block copolymers

Styrene–butadiene and styrene–isoprene block copolymers have rubber-like properties

The styrene–butadiene copolymer elastomer formulated with tackifying resins can be

Vinyl acetate copolymers

Vinyl acetate–ethylene copolymers for liquid applications

316 Printing materials: science and technology

include adsorption (1935), electrostatic (1950), diffusion (1960), molecular dispersion