adhesives

Chemistry
• Atoms bond together to form molecules.
• Molecules bond together to form solids.
• There are many different processes
through which this bonding occurs.
• The forces that cause bonding between
molecules in solids are also responsible
for adhesion between different materials
when they are glued together.
Ionic bond
The alternate positive and negative ions in
an ionic solid are arranged in an orderly
way in a giant ionic lattice structure shown
on the left. The ionic bond is the strong
electrical attraction between the positive
and negative ions next to each other in the
lattice. The bonding extends throughout
the crystal in all directions.
The atom losing electrons forms a positive
ion (cation) and is usually a metal.
The atom gaining electrons forms a
negative ion (anion) and is usually a non-
metallic element.
 Metallic bond

• The crystal lattice of metals consists of ions (NOT atoms!) surrounded by a

'sea of electrons' forming another type of giant lattice.
• The outer electrons (-) from the original metal atoms are free to move around
between the positive metal ions formed (+).
• These free or 'delocalised' electrons are the 'electronic glue' holding the
particles together.
• There is a strong electrical force of attraction between these mobile electrons
(-) and the 'immobile' positive metal ions (+) and this is the metallic bond.
• This structure is why metals are good conductors of electricity and heat.
 Covalent bond
• Covalent bonds are formed by atoms sharing
electrons to form molecules. This type of bond
usually formed between two non-metallic
elements. The molecules might be that of an
element i.e. one type of atom only OR from
different elements chemically combined to form a
Here Carbon (2,4) compound.
shares outer electrons • The covalent bonding is caused by the mutual
with Oxygen (2,6) electrical attraction between the two positive
nuclei of the two atoms of the bond, and the
Each atom now has
electrons between them.
the “illusion” of having
8 outer electrons, • One single covalent bond is a sharing of 1 pair of
which is a low energy electrons, two pairs of shared electrons between
state. the same two atoms gives a double bond and it is
possible for two atoms to share 3 pairs of
electrons and give a triple bond.
Intermolecular bonding – Van der Waals forces
Molecules overall are electrically neutral, but their charge
distribution can vary. If the electrons bunch together at one
side that side becomes negative, the other positive. This is
called a temporary dipole. Some molecules (e.g. HCl) form
permanent dipoles. (see hydrogen bonds)

Dipoles give rise to intermolecular attractions

Imagine a molecule which has a temporary polarity being
approached by one which happens to be entirely non-polar
just at that moment. ( In reality, one of the molecules is likely
to have a greater polarity than the other at that time - and so
will be the dominant one. )
As the right hand molecule approaches, its electrons will tend
to be attracted by the slightly positive end of the left hand one.
This sets up an induced dipole in the approaching molecule,
which is orientated in such a way that the + end of one is
attracted to the - end of the other.
Van der Waal forces
An instant later the electrons in the left hand molecule
may well have moved up the other end. In doing so,
they will repel the electrons in the right hand one.
The polarity of both molecules reverses, but you still
have + attracting -. As long as the molecules stay
close to each other the polarities will continue to
fluctuate in synchronisation so that the attraction is
always maintained. This synchronised movement of
the electrons can occur over huge numbers of
molecules.

This diagram shows how a whole lattice of molecules

could be held together in a solid using Van der Waals
dispersion forces. An instant later, of course, you
would have to draw a quite different arrangement of
the distribution of the electrons as they shifted around
- but always in synchronisation.
Hydrogen bond
Water has a simple molecular structure. It is composed of one
oxygen atom and two hydrogen atoms. Each hydrogen atom is
covalently bonded to the oxygen via a shared pair of electrons.
Oxygen also has two unshared pairs of electrons. Thus there
are 4 pairs of electrons surrounding the oxygen atom, two pairs
involved in covalent bonds with hydrogen, and two unshared
pairs on the opposite side of the oxygen atom. Oxygen is an
"electronegative" or electron "loving" atom compared with
hydrogen. Water is a "polar" molecule, meaning that there is an
uneven distribution of electron density. Water has a partial
negative charge ( δ+ ) near the oxygen atom due the unshared
pairs of electrons, and partial positive charges (δ- ) near the
hydrogen atoms.
An electrostatic attraction between the partial positive charge
near the hydrogen atoms and the partial negative charge near
the oxygen results in the formation of a hydrogen bond as
shown in the illustration. The ability of ions and other molecules
to dissolve in water is due to this polarity.
 Important mechanisms of adhesion:

Mechanical adhesion
(adhesive locks into flaws scratches etc and anchors surfaces together)
Adsorption (usually the most important mechanism)
(intermolecular forces are responsible for adhesion)
Chemisorption (chemical bonds tie materials together)
Electrostatic attraction
(surfaces become charged oppositely and therefore attract)
Diffusion (adhesive blends in to surface)
 Mechanical adhesion

The mechanical interlocking theory of adhesion states that good adhesion occurs when
an adhesive penetrates into the pores, holes and crevices and other irregularities of the
adhered surface of a substrate, and locks mechanically to the substrate. The adhesive
must not only wet the substrate, but also have the right rheological properties to
penetrate pores and openings in a reasonable time.

This theory explains a few examples of adhesion such as rubber bonding to textiles and
paper. Since good adhesion can occur between smooth adherend surfaces as well, it is
clear that while interlocking helps promote adhesion, it is not the only mechanism
involved in adhesion.
 Diffusion theory

The intrinsic adhesion of high polymers to themselves, or to each

other, is due to mutual diffusion of polymer molecules across the
interface. This requires the macromolecules or chain segments of the
polymers (adhesive and substrate) possess sufficient mobility and are
mutually soluble (possess similar values of the solubility parameter).
Works in the same way as a weld or brazed or soldered joint.
 Electronic theory

The basis of the electrostatic theory of adhesion is the difference in

electonegativities of adhesing materials. Adhesive force is attributed to
the transfer of electrons across the interface creating positive and
negative charges that attract one another. For example, when an
organic polymer is brought into contact with metal, electrons are
transferred from metal into the polymer, creating an attracting electrical
double layer (EDL).
Adsorption theory
Proposes that, provided sufficiently
intimate intermolecular contact is
achieved at the interface, the material
will adhere because of the surface
force acting between the atoms in the
two surfaces, the most common such
forces are Van der Waals forces and
are referred to as secondary bonds.
The process of establishing intimate
contact between an adhesive and the
adherend is known as wetting.
The figure shows good and poor
wetting of a liquid (epoxy adhesive)
spreading over a surface.
 Chemisorption

The chemical bonding mechanism suggests that primary

chemical bonds may form across the interface. Chemical
bonds are strong and make a significant contribution to the
intrinsic adhesion in some cases. Coupling agents and
adhesion promoters are often used to help in fixing the
adhesive at the surface by chemical reaction.
 Table 1    Comparison of the bond energy of different type of tractions [2,3]

Bond energy ( kJ / mol )

Type
Ionic 590 ~ 1051
Covalent 63 ~ 710
Metallic 113 ~ 347
Permanent Hydrogen bonds involving fluorine < 42
dipole-dipole
Hydrogen bonds excluding fluorine 10 ~ 26
interactions
Other dipole-dipole (excluding hydrogen bonds) 4 ~ 21

Dipole-induced dipole <2

Dispersion (London*) forces 0.08 ~ 42

       *: London force is one kind of Van der Waals forces.

 Traditional glues:
ANIMAL AND VEGETABLE GLUE
There are two basic types of natural adhesives which are
commonly used: animal and vegetable. A wide variety of
vegetable glues are derived from starches, gums,
cellulose, bitumen and natural rubber, and have
specialized applications. Animal glues are derived from
casein (a milk protein used in paint), blood albumen
(used in plywood), and collagen (used in woodworking).
All of these adhesive products are organic in nature and
non toxic to humans.
Animal glues are adhesives which are essentially high
polymer proteins derived from hydrolyzed collagen.
• Animal hide and bone glues set in a two part process which first
begins by cooling from 145 degrees to room temperature, and then
completely drying by evaporation during the next 12 to 24 hours.
This allows the traditional woodworker to use this glue to his
advantage, since hammer veneering and "rubbed" joints both
require a glue with a rapid initial grab as it cools. In addition, the
strong initial hold of these glues allows clamps to be removed and
reused on another job while the first project dries overnight.
• Protein glues form a chemical (molecular) bond as well as a
mechanical bond. This means that fresh animal glue will reactivate
and chemically bond to previous animal glue surfaces, as well as
forming a strong mechanical bond with wood surfaces and other
natural fibers. Hide glue sticks to surfaces by an electrochemical
attraction, or "specific adhesion." It is one of the few truly reversible
glues, which can be changed from liquid to solid and back again
with the addition or subtraction of heat and moisture.
 What different types are there?
Water based  Solvent Based  Chemical curing

Water based adhesives are made of natural or synthetic polymers, mixed in

water, and are used when one of more surface is porous
(e.g. wallpaper paste). They are slow to dry and will not stick non-porous
materials like plastic. Water based adhesives are typically made of Water -
Polymer - Thickener - Additives to improve strength - Biocide which stops
them fading in strength with age.

Solvent based adhesives are a synthetic adhesive polymer mixed in solvent.

They are used to stick non-porous surfaces and are fast drying.

Chemical curing adhesives involve creating a chemical reaction, and

sometimes this involves the use of an additional ingredient as a 'hardener'.
They are particularly powerful and are also fast bonding. As well as two-
pack adhesives like Araldite the silicone adhesives are also in this group,
and the curing process requires the absorption of water as vapour.
 Do they all stick one surface
directly to another?
No. There are two general types of bonding
- direct and contact. In direct bonding the
adhesive is applied directly between two
surfaces. In contact bonding, you apply a
layer of adhesive to each surface, and
then the two layers of adhesive are put in
contact to stick to each other.
 Superglue is new, but surely the
process has been around a long time?
Yes, the Ancient Egyptians and the Romans
were the first to come up with practical
adhesives.
 
They used ground animal bones, flour and
water. Modern adhesives based on
plastics were only developed this century.
 
 Casein adhesive
Did you know you can make glue quite easily yourself, and main
ingredient is milk! Here is the procedure for making your own glue:

• Pour about 50ml of skim milk into a beaker. Add 10ml of vinegar
(acetic acid).
• Heat slowly on a hot plate with constant stirring. As soon as the milk
begins to curd, remove the beaker from the heat. Continue to stir for
about one minute.
• Filter mixture.
• After the liquid has been drained, scrape the curds from the filter
paper into the beaker.
• Add a little water and .5g of sodium bicarbonate (baking soda). Stir
the mixture until it is creamy smooth. If it still bubbles, add a little
more baking soda to completely neutralize the vinegar.
 P.V.A. (polyvinyl acetate)
There are two types interior and exterior. Both are used
for sticking wood to wood, also for other porous materials
such as paper, and for wallpapering – priming walls and
putting up borders.
Interior does not hold when it gets wet so anything to be
made for outside needs exterior. Exterior is far more
expensive than interior so you wouldn’t use it for an inside
piece of work. These glues need to be left overnight to dry.
PVA is also used for varnish for interior woodwork.
To look at it is a thick white cream.
 EPOXY RESIN
(e.g. Araldite).
These glues are two separate substances which
do not harden unless you mix them together. Once
mixed they will stick almost anything, wood to
wood, metal to wood, wood to plastic, ceramic pots
and so on. They are very expensive so you
wouldn’t use them if there was something cheaper
you could use. These glues will harden in less than
15 minutes. To look at these substances are thick
sticky liquids one which is clear and one which is
yellow.
 RESIN WOOD GLUE
Cascamite
Only used for sticking wood to wood,
excellent for underwater use. Will fill small
gaps. Usually comes in powder form and is
mixed with water. Dries clear like glass.
 IMPACT and CONTACT ADHESIVES
• RUBBER based solutions which are applied to both
surfaces. they are left to dry for about ten minutes and
the surfaces brought together. The sticking is instant and
you do not have time to ‘adjust’ work. Used for sticking
tiles to floors, plastic laminates to kitchen surfaces and
vinyl backed upholstery. These glues look like ‘runny’
rubber with a dangerous smell which can kill.

• LATEX This type of glue is excellent for sticking most

types of materials together. You put glue on both
surfaces and allow to become touch dry then put the
surfaces together.
 POLYSTYRENE CEMENT
Consists of polystyrene dissolved in a solvent to form a
nearly saturated solution. It works by dissolving the
surfaces of the work pieces, then as the solvent evaporates
a real weld is formed.
This glue is not particularly strong, but is ideal for sticking
plastic to plastic when the joints are not going to be
‘knocked about’. Used for making models mainly.
A similar glue can be made for joining acrylics such as
PERSPEX together, simply by dissolving small pieces of
perspex in acetone or amyl acetate.
“Superglue” Cyanoacrylate (C5H5NO2).
Cyanoacrylate is an acrylic resin in the form of a thin clear liquid. It
forms a strong bond almost instantly. All it requires is the hydroxyl ions
in water to trigger the process, and it is just the case that almost any
object you might wish to glue will have at least trace amounts of water
on its surface. Super glue, undergoes a process called anionic
polymerization . The Cyanoacrylate molecules start linking up when
they come into contact with water, and they form in chains to make a
durable plastic mesh. The glue thickens and hardens until the
molecular strands can no longer move.

Even more expensive than epoxy resin, these glues will stick most
surfaces which are fairly smooth and which will not allow the glue to
‘soak in’, such as glass, metal, plastic. They can also stick skin so you
have to be careful. Once the glue is applied a slight pressure for about
10 seconds will produce a very strong joint.
No More Nails
UniBond No More Nails is a super strong instant grab gap
filling adhesive that sticks virtually anything to anything!
Multi-Purpose Solvent Free
Safe to use Fills minor gaps in uneven surfaces.
Dries white Overpaintable

No More Nails is ideal for fixing

· Skirting boards · Dado rails
· Worktops · Architraves
· Decorative wall panels
· Plasterboard Covings
· Carpet and carpet grippers

UniBond No More Nails Bonds:

Wood· Plaster· Brick· Ceramics· Metal· 
Glass· Concrete· Cork· uPVC
 How a glue stick works
• When an adhesive is pasted on the surface of a material (adherend), the adhesive
penetrates into the small gaps on the adherend surface, and then hardens and does
not move any more inside the gap. It is thought that this inability to move is one of the
reasons that things attach together. This effect is called the “anchor effect“, because
like a ship with a dropped anchor the adhesive does not move. There are chemical
bonds between adhesive molecules and adherend molecules, which also make them
stick together. These bonds are, for example, hydrogen bond, Van der Waals bond,
ionic bond, and covalent bond.
  
Thus, adhesion occurs not as a single effect but as the sum of several effects
above. Polyvinyl pyrrolidone (PVP), the major component of a glue stick, also
adheres by several effects such as anchor effect and intermolecular forces. There are
also hydrogen bonds (O=C∙∙∙∙∙OH － ) between carbonyl groups in PVP and hydroxyl
groups in paper. 
 
On the other hand, since the attraction force is generated when one molecule comes
close to another molecule, it is necessary that the adhesive is brought near to the
solid surface by liquid. Because the penetration of the adhesive into the adherend
surface is important for adhesion, and the strength of adhesion depends on several
effects above, we cannot always say, “to feel sticky = to have adhesive force”.
 Hot melt glues
• These are gap filling adhesives
Adhesive tapes
Adhesive tapes use an acrylic or rubber
based adhesive on a polyester, paper,
polypropylene or vinyl film. Can be single
or double sided.
High strength VHB (very high bond) tapes
are used in applications that require
strong, permanent bonds with high shear
and peel adhesion.  These products are
most suitable for heavy industrial use or
external environments. 
VHB tapes distribute stress along the
bond-line.  The 'viscoelastic' nature of the
solid glue system allows for the adhesive
to flow into the microscopic surface of the
material to be bonded thus providing
100% 'wet out', resulting in much greater
bond performance.
Parameters affecting environmental resistance:
Water is the most commonly encountered environmental that gives the greatest problems in the
environmental stability of adhesive joints. The great majority of bonded structures are exposed to
moist air, and if the relative humidity is high then over a period of time the strength of joints usually
declines. The properties of adhesive are very sensitive to water, and this is come from the fact that
adhesives are hydrophilic. The polar groups that confer adhesive properties on a substance also
make them hydrophilic.
 
1. Concentration of water:
The higher the water concentration, the more rapid and greater the degree of attack.
Furthermore, there often appears to be a minimum concentration below which no environmental
failure, or at least no significant attack over a comparatively long time-scale, occurs.
2. Temperature: increasing the temperature of the environmental increases the rate of strength loss.
3. Adhesive type
4. Adherend type
5. Adherend surface pretreatment
6. Applied stress:
The rate of loss of strength will be faster if a tensile stress and shear stress is present.
7. Joint design
 How does glue work?
If two objects can come very close to one another (and I
mean *very* close -- less than an atom's-width apart) then
the individual atoms often tend to bond with one another.
The bond is an electrical phenomenon, or more broadly put,
an electromagnetic phenomenon. In theory, if I could cut a
steel bar in half and produce two perfectly smooth faces,
when I put the faces back into contact, they would adhere to
one another with great force, as if they had been super-
glued.
In the real world, though, the steel faces are never perfectly
smooth, or even close to it. There are billions of tiny
imperfections that prevent the two faces from meeting
perfectly, so that there are large (to an atom) gaps between
the faces. As a result, they won't stick together.
But if you take two pretty flat items -- two sheets of
glass, for instance -- and sandwich them together
with just a tiny bit of water, they will stick together
with amazing tenacity. The water fills in the gaps,
and helps the glass surfaces come into close
enough contact that their own electromagnetic
forces can make the two panes of glass adhere.
The water is acting as a glue. And this is how glue
generally behaves whenever two items are pasted
together.
 Rough and smooth
If you look at most surfaces
through a microscope, you
will find that they are not
smooth.
What an adhesive does is
fill in the gaps and build a
bridge between two
surfaces.
The adhesive must then
harden, so that the bond
stays together.
 Links
http://www.gluegunsdirect.com/oldsite/oldsite/gg.latestnews.adhesivevs.html

http://home.pacbell.net/ebeniste/gluearticle.htm

http://cms.3m.com/cms/GB/en/2-37/kcFlrFV/view.jhtml

http://www.chemguide.co.uk/atoms/bondingmenu.html#top

http://campus.umr.edu/piezo/MotorAnalysis/BondingNote/BondingNote.html

http://www.specialchem4adhesives.com/resources/adhesionguide/index.aspx?id =