5 - 5 - Week 5B - 1 Introduction to Polymers & Fibres (17_31).txt

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So this lecture is about polymers and
fibres.
Before we can understand how polymers and
fibres can be used in forensic science,
we first need to know a bit about
the chemistry of polymers and fibres.
So what is a polymer?
Well, if you take a small molecule and
then you link it to another one
of the same small molecule, and
then to another one, and then to another
one, and then to another one and so on,
you end up with a long
chain molecule made up
of those original single
molecules linked together.
So, those original single molecules
are known as the monomer and
this long chain molecule
is known as the polymer.
Poly of course comes from the Greek for
many.
Now, not all polymers consist of same
monomer over and over and over again.
We can mix up different monomers.
For instance, if you have two different
monomers, then when you link them up
to make a polymer, you can get what 
we call a co-polymer,
where the two have been combined to
make a single long, long molecule.
The main thing to understand
is that a polymer is made up
of long chains of these
individual monomers.
So here's an example of a very common
polymer that we all encounter everyday
in our lives, and that's polyethylene,
which is better known as polythene.
So polythene is the polymer
derived from the gas ethylene, so
every year millions of tons of ethylene
are polymerized to make polythene for
all sorts of uses including of
course, things like shopping bags.
We're also familiar with polymers
like polypropylene and polystyrene.
Polystyrene, of course, is the material
that's used to make styrofoam packaging,
and these are polymers from the 
corresponding monomers, propylene and
styrene, and its done in a quite similar
way to the polymerization of ethylene.
Now polyethylene, polypropylene, polystyrene
are widely used to make all sorts of
things but they're not actually good for
making fibres, so people don't make
fibres out of these particular polymers.
Here's a polymer that is excellent for
making fibres.
It's nylon.
And nylon is a co-polymer,
where you take two quite different
compounds and induce them to form a chain.
So nylon-6,6, there are different
forms of nylon, but nylon-6,6
comes from adipic acid polymerised
with diaminohexane, and if you count up
the atoms you'll realize that molecules of
water are being produced as a by-product.
It's nylon-6,6 because adipic
acid has six carbon atoms and
diaminohexane has six carbon atoms.
And you can see it forms a polymer where
you have alternating adipic acid and
diaminohexane units.
And nylon, as I mentioned, is an excellent
polymer for making fibres and
probably at this very moment, all of us are
wearing something containing some nylon.
So, suppose we have a fibre
found at a crime scene.
What could you do with
that fibre to identify it?
Well, the simplest thing you can do is
just to look at it under the microscope,
and this may help you determine the type of fibre.
For instance, whether it's wool or
nylon or cotton or some other.
Now because we can consider
fibres as organic chemicals,
we can also use on them the 
spectroscopic techniques that we
studied in an earlier lecture.
So you will use spectroscopy on the fibres
to determine their chemical composition.
Microscopy, you can also look at physical
features such as the shape of a fibre.
Now, some fibres, specifically
the synthetic fibres, the shape is
characteristic of the manufacturing,
which we'll talk about in a moment.
Now, most fibres are going to be colourless.
Most synthetic fibres will
originally be colourless,
but we like to have coloured
fibres in our clothes,
so a dye has to be added to the synthetic
fibres to give them those colours.
So, not only can we do spectroscopic analysis to
determine the chemical nature of the fibre,
we can also do spectroscopic analysis to
determine the chemical nature of the dye,
and this, of course, will be another step
towards individualization of that fibre.
The manufacturers also add other chemicals to
the fibres to make them attractive for
use in clothing.
For instance, one kind of chemical
that's added are called delustrants,
and these are to make the fibres less shiny.
So again, we can use chemical spectroscopic methods
to identify the delustrant.
And the more different chemical components
of the fibre that we can analyze,
then the better we can get towards
individualization of that fibre.
Obviously there's going to be a
difference between natural fibres and
synthetic fibres.
Natural fibres coming from plants and animals;
synthetic fibres coming from the chemical industry.
So, let's take a quick look at making
synthetic polymers and synthetic fibres.
Synthetic polymer fibres are typically
made by a process called extrusion.
So on one side of a barrier,
there is a polymer either in
it's molten state, or in solution,
so it's a liquid form.
The barrier is permeable, there are holes
in it. So when the liquid form of
the polymer is forced through the barrier
into a new medium where it solidifies,
as it goes through these holes, it will
form fibres, and this is called extrusion.
And synthetic fibres are typically
made by extrusion processes.
So clearly, the shape of the fibre and
the size of the fibre are going to depend
on the hole that the material was forced
through when the fibre was formed.
This will vary from manufacturer to manufacturer.
So if you have a synthetic fibre, you
can look at it under the microscope and
the shape of the fibre will help
you identify which manufacturer, and
perhaps, which batch of material when it was made.
I mentioned that we can also
identify the chemicals that make up
the fibres using spectroscopic methods,
and a very good method for doing
this is from the infrared spectrum.
Now, the normal infrared spectrum
is recorded on a fairly large amount of material,
but a fibre found at a crime scene 
would be just a single fibre,
so we have to use what is
called a IR microscope.
And this combines a microscope,
that is so you can see the fibre,
and the IR spectrometer.
And this combination of
the IR microscope allows
the analysis of the chemical
constituents of the fibre.
So this is the infrared spectrometer that
I use for lecture demonstrations.
Most infrared spectrometers
are very sensitive machines and
you can't move them,
but this one's very robust and
I can pick it up and
carry it across campus and
use it for lecture demonstrations.
It's not the kind of machine that
a forensic scientist would use for
fibre analysis,
and that's because it's just an ordinary infrared.
It's not an IR microscope.
So, we're not going to be using
the tiny little fibre samples
that might be collected at the crime scene.
We're going to be using some
slightly bigger pieces of string.
So I have two samples here.
One of these is
genuine wool, one of these is synthetic wool,
and an ordinary person just by
inspection really wouldn't be
sure which one was which.
But we're going to use
the infrared spectrometer to prove
the identity of these two.
This machine here works by reflectance.
The IR beam is generated right here, and
it reflects off this little window right here.
And so what we're going to do is press
the sample against that little window.
So, this is the IR spectrum from
some of that first sample and
an important band to look at is this one here.
We can see a strong absorbance at 1624 wavenumbers
and we know that this kind of absorbance
is characteristic of the stretching of
the carbon oxygen bond in a protein.
Now wool, of course, is a protein.
Wool is made of protein.
We can conclude that this
sample is genuine wool.
Now let's analyze the second sample.
So if we look at the IR spectrum of the second sample,
which is the green trace on the screen,
we can see there's a signal at that
absorbance, but it's shifted.
We can now see that the carbon oxygen
stretching absorbance is coming at 1729.
This is not where you expect to
see this absorbance when you're
dealing with a protein.
So clearly, this second sample is not
real wool and it probably is polyester.
And if we look a little bit further at
the spectrum, we can see there's another
band just here at 2241, and what this is telling us
is that this fibre sample is probably some
kind of blend of different polymers, and
this second absorbance here at 2241
is probably a nitrile polymer.
Our infrared spectrometer is not
limited to analyzing fibres.
We can analyze just about anything that
we can put into that sample holder.
So here, I have two dollars,
two Singapore dollars.
Now, money is normally made of paper
but this is not, this is a polymer note
and we can analyze this using infrared.
This is the spectrum of the Singapore $2 note,
and you can see that it shows an 
absorbance at 1714 wavenumbers,
which is quite similar to the polyester.
So these bank notes are not made of paper,
they're made of polymer, and
it's telling us that at least one of
the polymers in this bank note is quite
similar to that second fibre sample.
So this is the Singapore $50 note.
So let's use infrared spectroscopy
to find out what this is made of.
So if I put
the $50 note,
so the red trace is the spectrum
of the $50 note and
you can see that there's
almost no absorbance in
the region about 1700 wavenumbers, but
there's a big absorbance
in the region of about
3200 to 3300 wavenumbers.
This is because our $50 is still made of paper.
Paper is made of cellulose, it doesn't
have any C double bond O in its molecule,
so there's no absorbance in the same area
where we saw the polyester absorbing. But
cellulose has lots of hydroxy groups
with O bonds, and these absorb
in that region above 3000 wavenumbers,
and that's what's responsible
for this absorbance that's
indicated at about 3200.
So using the infrared spectroscopy,
we can very quickly tell what these
different things are all made of.
Here's one example of a case
where the I...
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