MSE 470/MAE455 Polymer Thermal Mechanical Properties Slide Guide Tutorial

In these notes, we will learn about how the chemical structure and
morphology of polymers affects their mechanical and thermal
properties.

This concept map gives an overview of polymers. This is intended

to be a guide of how different concepts are connected, and the major
points within the topics. The three major topics shown here are:
1) polymer morphology
2) polymer synthesis, classification, and examples, and
3) polymer processing and examples

Use this slide to help learn more about classifying polymers. This
slide shows 4 main categories of polymers based on similarities in
morphology and mechanical properties. The 4 include:
1) 1-D thermoplastic amorphous polymer (with no structural order)
2) 1-D thermoplastic semicrystalline polymer (amor. + cryst areas)
3) 3-D lightly covalently crosslinked polymer, or elastomer
4) 3-D heavily crosslinked polymer or thermoset
The pictures are items made from each corresponding type of
polymer morphology. However, sometimes more than one kind of
polymer can make similar items, (like PE or PP bottles) and it is up
to you to decide which one has the properties that best make up a
given item.

Recall stress strain graphs from mechanical properties of metals.

*A is a heavily crosslinked thermoset resin, (bakelite) where 25C is
far below its Tg (200C). It has the highest E (due to covalent
bonding) and is strong, but has little ductility and is brittle.
*'B' is an amorphous thermoplastic polymer, PS, which at 25C is far
below its Tg of 100C and therefore has moderately high E (but lower
than A) but is not as strong (no covalent crosslinking) and is brittle.
*'C' is a semicrystalline thermoplastic polymer, polyethylene, which
at 25C is above its Tg but below its Tm. The amorphous regions,
which are very flexible but are held together by the crystalline
material, provide much ductility although the E is not as high as 'B'
since the amorphous regions are quite flexible.
*'D' a lightly crosslinked elastomer much above its Tg giving low E
and high elasticity with the low density of covalent crosslinks.

We will be using the Log E versus T curve to relate thermal to mechanical

properties for different types of polymers. Important temperatures for each type
of polymer are T25C (room temp.), Tg (glass transition temperature), and Tm
(melting temp. of semicrystalline polymers).
There are 4 main regions:
I) glassy, where polymers are below Tg and are stiff and brittle;
II) leathery, where polymers are in the vicinity of the Tg and are somewhat
flexible with some ductility,
III) rubbery which begins just above Tg and polymers are relatively flexible and
ductile but have lower stiffness;
IV) viscous, is the region where amorphous thermoplastic polymers become
soft and sticky, but semicrystalline polymers retain their shape, because of the
crystalline lamallae and tie molecules, up until it reaches Tm.
3-D crosslinked polymers retain their shape above Tg and degrade at 200C to
350C. Learning to identify a polymers Tg and T25C on this graph helps you
understand that polymers thermal and mechanical properties.

Polymers are extremely sensitive to temperature. One way to express

this sensitivity is called the Log Modulus vs. T curve. These graphs
will vary depending on the type of polymer being plotted ( thermoset,
amorphous thermoplastic, semicrystalline thermoplastic, lightly
crosslinked elastomer). This graph shows a thermoset, bakelite, which
is in the glassy region at 25C and is far below its Tg of 200C. It has the
highest E (due to covalent bonding) and is strong, but has little ductility
and is brittle.

Log E vs. T for an Amorphous Thermoplastic, PS, polystyrene, which is

in the glassy region at 25C is far below its Tg of 100C. It has the next
highest E (after the covalently bonded thermoset) and also has little
ductility and is brittle. At temperatures above its Tg it becomes leathery,
rubbery, and viscous after temperature exceeds its Tg.

Log E vs. T for a Semicrystalline Thermoplastic such as PE,

polyethylene, a semicrystalline thermoplastic polymer, which at 25C is
above its Tg but below its Tm. Semicrystalline polymers have an
amorphous component, and a chain folded crystalline component. The
chain-folded polymer has crystalline lamellae. The polymer strand
that links the two lamellae is called a tie molecule The amorphous
regions are very flexible but are held together by the crystalline material
and tie molecules, provide much ductility although the E is not as high
as 'B' since the amorphous regions are quite flexible.

Log E vs. T for a Lightly Crosslinked Elastomer, polybutadiene, has a

very low Tg of -100C and 25C: lies at a low value in the rubbery
region. What this says about the polymers properties: Some covalent
bonds providing a low degree of crosslinking contributes to 3-D
stability. It has much lower modulus than all of the other types of
polymers.

This slides shows how to draw curves for the four types of
morphology in the vicinity of Tg (the glass transition temperature)

Tg

Tm

Hands-on activity: Take a plastic cup. The recycle image on the

bottom of the cup is a number 6, which corresponds to polystyrene
(PS). The cup was formed by the vacuum thermoforming process.
Chances are that the polymer chains are somewhat aligned. So, in
which direction will the deformation occur if you try to deform the
cup? When the cup is crushed in your hands, observe the way it broke.
The cups break along vertical lines. Where it doesnt break, it turns
white, and this is called crazing. Along the white area, there is light
scattering due to elongated voids.
Overall, the morphology changes that occur upon deformation are
shown for each type of the four characteristic morphologies.

The chemistry and structure of polymers strongly affects their thermal

properties and thus their mechanical properties. For addition (or free
radical) polymers the size of the "substituent" attached to the mer unit
on the side of the polymer chain dramatically affects Tg. The larger
the substituent (an element or chemical group), the more thermal
energy is required for the chains to rotate in order to reach their Tg.
This is what increases a polymers Tg .
For example, when a small atom like hydrogen is the substituent
(polyethylene), Tg is low, -90C. But adding a large substituent atom
(like Cl in PVC), Tg is high, 100C.

For condensation (or stepwise) polymers, stiffer characteristic linkages

between mers or stiffer chemical units within a mer (e.g. phenyl groups)
will require more thermal energy to reach the Tg. This graph shows
which linkages are stiffer. So, the stiffer the linkage, the more thermal
energy that is required for rotating polymer chains. Again, requiring
more thermal energy to rotate chains means that polymer will have a
higher Tg.

A phenyl group (or benzene ring) within mers along the main chain
acts to stiffen the chain, as can be seen for the examples shown in the
slide. This is yet another factor responsible for increasing a polymers
Tg.

The same factors that give a polymer a high glass transition temperature
also raise the melting temperature.

An example of the effect of strain rate on polymer properties comes

from a story of camper who struck a polypropylene camping stake with
a hammer at a cold temperature, it splintered, and a splinter flew into
his eye. With a slower rate of leading the polymer was in its rubbery
region, but the high rate of impact of the hammer moved the log E vs. T
curve to the right so that ambient temperature was then in the glassy,
brittle region. If a polymer is at a temperature below its Tg, it loses
ductility and can behave the way the cold camping stake did.

Plasticizer can be used with PVC to shift its Tg. The plasticizer is a
liquid with small molecules that are compatible with PVC and are
readily taken up by the polymer. The small molecules help move the
polymer chains away from each other, thus making it easier for the
chains to rotate and thereby lowering Tg.
* With 0% plasticizer PVC is far below its Tg of 100C and at 25C is
stiff and rigid in its glassy region and can be used for plumbing pipe.
* With 30% plasticizer PVC is near its glass transition at 40C and at
25C room temperature is in its leathery region and is suitable for use
as floor tiles.
* When PVC has 50% plasticizer it is in its rubbery region and is very
flexible and ductile and is suitable for beach balls, small swimming
pools, and car seats.

Crosslinking diene-type elastomer polymers can have a dramatic

effect on the elastomer properties. Higher degrees of crosslinking
move the Tg to higher temperatures as well as increasing the stiffness
and strength but also lowering ductility. These effect can be seen in
the two graphs. If the ambient temperature goes down and begins to
approach the Tg the elastomer will go through the rubbery region into
the leathery region. The Challenger O-Ring is an example. The O-ring
was too close to its glass transition temperature. It lost elasticity at
those temperatures and did not spring back into position quickly
enough when stressed. It did not seal hot gases from escaping the main
body, thus causing the Challenger disaster.

In this activity, try drawing the Log E vs. T curve and the Stress-Strain
curves for the given polymer examples.
The plastic cup is polystyrene (PS), which is an amorphous
thermoplastic.
The milk jug is made of polyethylene (PE), which is a semicrystalline
thermoplastic.
The tire could be made of polybutadiene or polyisoprene, which are
lightly crosslinked elastomers.

This summary slide goes over the highlights of this lecture on polymer
thermal and mechanical properties.