Lecture 1

Classic mechanics when applied to an atom only holds for 1 electron. If even 2 electrons are
added it breaks down. One reason for this is that classic mechanics does not account for the
angular momentum of electrons
Figure 1: Atom and Energy Level Representation
Electrons generate two magnetic fields each and arrange themselves in such a way as to
neutralize each other. To fully explain this an understanding in quantum mechanics is
needed
Momentums of electrons cancel out that of nucleus. This leads to a very stable, low
potential energy structure
Two things react together if they are relatively unstable and joining would lower their
potential energy by reducing the electric field intensity or joining electrons due to their
magnetic fields
If a change in magnetic field is prevalent the resulting bond will be covalent while if the bond
is due to electronegativity the bond with be ionic
Ions are produced because they are hybrids between bonds due to electronegativity and
magnetic differences

Chemical Bonds

Figure 2: Dipoles and Bond Depth

Primary Bonds

Figure 3: Primary Bonds

Chemical thermodynamics can have a role in bond forming. For example a high temperature and
pressure we get diamonds as opposed to graphite
Figure Four: Long Chain
Metals:

Usually metals have a d energy level. If p and d levels make a hybrid you get 12, as opposed
to 3, lobes. So close are these lobes that if you try to deform the material the bonds break
and immediately reform. This is the reason for the sea of electrons and unidirectionality

Lecture 3

Polymers bound together by two, sometimes even 3, types of bonding

o Primary Bonding
o Secondary Bonding
o Sometimes even weaker primary covalent bonds and thanks to these we can achieve
possibilities previously thought impossible (like re-melting thermosets)
There are three kinds of engineering polymers:
o Commodity polymers
When free radical is formed a lot of energy is released
From mer to free radical is known as free radical polymerization and heat
and a catalyst (to reduce temperature needed) are used. By controlling the
temperature we control the structure of the polymer we get. Another
important factor for controlling is that once it starts the reaction is highly
exothermic so it is convenient to start with a lower temperature otherwise it
will get too hot and explode
If R in the functional unit with CH3 we produce polypropylene [PP] instead
of polyethylene [PE] which has a higher glass transition and can be used at
higher temperatures
If R is replaced with CL we get Vinyl as a functional unit and PVC
A particular characteristic of polymers made like this is that the resultant
polymers are inert (but still subject to UV degradation)
o Polymers formed by a condensation reaction
Stronger, Harder and easier to cast
Intrinsically chemically weaker because the reaction which polymerized
them is reversible by a de-polymerization process
Macro-molecules linked together by Wan-der-Walls forces
o Wan-der-walls forces originate because C has 6 protons while H has 1 and so
electrons sit closer to the carbon resulting in partial charges being generated in the
structure (polar bond)
o Each individual bond is weak but with increasing molecular weight the attraction
becomes significantly large giving the impression that one is dealing with a solid
however shorter chains act like waxes. Very short chains like propane and butane
the heat in the atmosphere vibrates these molecules strong enough to rupture these
bonds making a gas
The chains are formed by very strong bonds and so any movement is the macro-molecules
sliding past each other (Wan-der-Walls forces break and re-join)
A chain 8 carbon atoms in length is just enough to make a liquid and we get petrol, 16
carbon atoms a diesel is produced (takes much longer to evaporate then petrol and needs
more heat)
If free radical polymerization is done at higher temperature branched chains are achieved.
This is because when heat makes the molecules vibrate more and so the chain twists and
vibrates vigorously and touches its own backbone (back-biting) and so strips its own
hydrogen and a long branch forms. A backbone with branching will be short with the same

molecular weight. The branches inhibit secondary bonds and so will have lower mechanical
properties then the straight chain at low temperatures however the decrease of tensile
strength with temperature is slower and in some cases the graphs of SCMs and BCMs
interest and above that point BCMs are more efficient for those high temperatures since the
branches will cause an inhibition (branches entangle as vibration and movement increases)
in movement that is not present in SCMs.
For low temperatures SCM are preferred since they have a high TS at low temperatures and
also crystallize easier
However a large molecule with straight chains will be brittle. To solve it is plasticised (small
molecule chains inserted into the material. They sit between the macromolecules pushing
them apart and prevents some of the secondary bonds, decreasing hardness but increases
tensile strength and means more entanglement so strength is maintained at higher
temperatures)
If mers with unsaturated sites are used and we polymerize these mers, sites where reactions
can still take place are present. This is useful because a difunctional oligomer (a chain
between 1 or a few thousand carbon atoms in length) can be introduced and this chain can
anchor from both ends and so can bond with two macro-molecules leading to permanent
links. This process is known as linking. This produces thermosets and is irreversible. One
problem is that we have a reaction taking place with fluids that are extremely viscous and so
the reaction can only take place at high temperatures and if the number of unsaturated sites
are not all used during the process you have a site susceptible to reaction and so they
degrade in atmosphere. Oxygen reacts with the sites cutting the macro-molecules into
pieces. This problem results in the fact that once the material is injection moulded or
compressed the product has to be removed from the mould and put in an oven for a
number of hours to use all these bonds improving its degradation resistance. Degree of
cross-linking is controlled by the amount of difunctional chemical introduced and the time
for the reaction to take place.