Elastomers

Abstract
In this group research project you will investigate some of the fascinating properties of rubber both experimentally
and computationally. You will examine the thermodynamics of ideal rubber and devise a simple 1D computational
model of the polymer chains. Ideal rubber is, of course, a mathematical abstraction and so you will also investigate the
expansion of rubber in the laboratory and use this to decide whether or not real rubber can be treated as ideal. You
will investigate the expansion of rubber as a function of both load and temperature. Typically, the thermal expansion
coefficient of unloaded, non-ideal, rubber is small and, in this experiment, you will build a Michelson interferometer
to accurately measure the small changes in length. You will document your findings as a report written in the style
of a scientific paper from the APS journal Physical Review B.

Introduction

Rubber is an elastomer, or elastic polymer. It is an incredibly versatile material that is used in many
applications; from car tyres, to running shoes, to the pencil rubbers that first gave this material its name.
The properties of elastomers are remarkable and very different to almost any other solids. For example,
ideal rubber does not expand when heated. In fact, loaded rubber will actually contract if heat is applied.
Rubber is a particular type of elastic polymer formed by vulcanising latex, a natural extract from the rubber
tree. After vulcanisation (a procedure invented in 1839 by Charles Goodyear, of Goodyear tyre fame) the
long polymers of natural rubber are interlinked by sulphur compounds. Here we will describe the rubber in
terms of the polymer chains between these sulphur crosslinks: rubber is essentially a 3D zigzag structure
with freely rotating bonds that allow the polymer chains to change their length by coiling or uncoiling.
In most solids, the atoms or molecules are held in place by strong intermolecular potentials. These determine
the equilibrium state of the solid and, because each atom or molecule sits in a deep potential well, it can take a
great deal of energy to deform or expand a normal solid. The thermodynamics of most solids are determined
by the variation of internal energy with shape and size and this also determines the thermal expansivity of
the material. When heated most solids expand and this is because, with higher thermal energy, each atom
or molecule can oscillate further from its equilibrium position leading to an effective increase in volume.
In ideal rubber on the other hand, each polymer chain is free to rotate about its bonds and each chain can
therefore coil or uncoil without changing the internal energy, U . The internal energy of rubber is therefore
independent of the shape at constant volume and, like an ideal gas, rubber obeys Joules law: rubber can
stretch and un-stretch with no change in U . However, we know that when rubber is stretched we feel a
restoring force, so what is the origin of this force? The answer is that the force is entropic in nature.
When rubber is stretched the polymer chains uncoil and begin to align into a more ordered state with
correspondingly lower entropy. The force we feel is a direct result of the second law of thermodynamics:
the rubber is trying to pull back into a more disordered state where its entropy is a maximum. Again, this
behaviour is analogous (but opposite in sign) to the ideal gas.
1.1

Deliverables

To complete this group project you will need to research and understand some basic concepts of
Thermodynamics including the first law of thermodynamics, and entropy. You will also need to learn
about optics and the Michelson interferometer. The project is split into two parts, an experimental part
in which you will study the expansion of rubber in the laboratory and a theoretical/computational part in
which you will investigate the properties and the behaviour of ideal rubber. You will report your findings in
a single scientific paper. This will be written in the style of the American physical society journal, Physical
Review B [1]. Although this document contains a small amount of background it is essential that you study
many different sources to find all the information that you will need.

Theory: Thermodynamics of ideal rubber

The first law of thermodynamics is simply a restatement of the conservation of energy. It can be written as
F dl = dU T dS,

(1)

where F is the force acting over distance dl, dU is the change in internal energy and dS is the change in
entropy S at constant temperature, T . We will always work in quasistatic equilibrium, so the load F on the
rubber is always equal to the restoring force F generated by the rubber. Then,




U
S
F =
T
.
(2)
l T
L T
In Eq. 2 it is clear that there are two contributions to the load needed to stretch a substance, a contribution
related to the change in internal energy with respect to length and a contribution from the change in entropy
with respect to length. In most solids, the first term is large and the second negligible. In rubber (and the
ideal gas) the first term is negligible and it is the entropic term that is important.
The entropy is essentially a measure of the disorder of the system. For rubber, the entropy is large when
the polymer chains are coiled and tangled, and small when the rubber is stretched so that the polymer
chains uncoil and align. It is possible to obtain a good physical understanding of the entropy of rubber with
a simple 1-dimensional model of a single rubber molecule [2]. In this model we assume that we have N
links of polymer each of length b and that these links are randomly ordered in 1D so that each link points
either to the right or to the left. Clearly there are many different ways of arranging the links, and different
arrangements will give different lengths of polymer. This is identical to a random walk problem where you
take steps of length b randomly to the right or to the left and see how far you have travelled after N steps.

Figure 1: Left: 2D projection of a rubber polymer of 18 links, tangled in 3D. Right: 1D model of a rubber molecule.
The figure shows 1 possible arrangement of N = 8 links of length b, with total length l = 5b.

The entropy is related to the number of ways, W , in which each possible length of the rubber molecule can
be achieved. Each time the chains rearrange through random thermal motion each particular arrangement
of links will arise with equal probability but some particular lengths of chain can be obtained in many more
ways than others and so the random thermal motion will likely push the molecule into these most probable
lengths. The Boltzmann relation (which is inscribed on Ludwig Boltzmanns tombstone) relates the entropy
to W ,
S = k ln W,
(3)
where k is the Boltzmann constant.
In the random walk problem, the number of ways, W , of arranging N links with Nr links pointing to the
right and Nl = 1 Nr links pointing to the left is obtained simply from the binomial distribution,
W =

N!
.
Nr !Nl !

(4)

As the length of the 1D rubber chain is related to the number of links pointing in each direction,
l = b(Nr Nl ),

(5)

it is possible to relate the entropy to the length of the rubber chain. Then, from Eq. 2, the relation between
force, length and temperature can easily be deduced,
F = kT /lo .

(6)

where the stretch is defined by the ratio of the stretched length l to the equilibrium length lo , = l /lo .
In the1D problem, although the most probable length of the rubber chain is zero, the average length is
l0 = b N . Eq. 6 is the equation of state for ideal 1D rubber. It is analogous to the more familiar equation
of state for an ideal gas which relates the pressure, volume and temperature.
2.1

Tasks
Investigate the random walk problem computationally. Devise a computational model to
calculate the length of a 1D rubber molecule after aligning its N links randomly to the right or the left.
Investigate the distribution of lengths as a function of N and find the most probable configurations.
What is the distribution function in the limit of large N ? How does the shape of the distribution
function change with N ?
If you programme in C you may need to use the pseudo-random number generator from the standard
library. The following C-code fragment will print an integer pseudo-random number between 0 and the
system variable RAND MAX.
#include <stdlib.h>
#include <stdio.h>
#include <time.h>
int main(){
srand(time(0)); /* initialise pseudo-random number generator */
printf("%d\n",rand()); /* random integer between 0 and RAND_MAX */
}
Derive and investigate the equation of state for ideal rubber. By combining basic
thermodynamics (Eq. 2) with your understanding of the random walk problem and the Boltzmann
relation you can derive the equation of state for rubber. You should investigate the equation of state
of ideal rubber and understand how the entropy, force, length and temperature are related.
Note: the one dimensional random walk model enables us to understand the majority of the physics
of ideal rubber, but in a full 3D model there are some small changes in the relation between entropy
and length and hence in the equation of state. The Guth-James equation of state for 3D rubber [6] is
F =

kT
( 1/2 ).
lo

(7)

Stirlings approximation, ln N ! = N ln N N, may be useful.

Experiment: Expansion of loaded rubber

Eq. 6 predicts that the stretch, , of ideal rubber is directly proportional to the load and inversely
proportional to the temperature.
This can easily be tested experimentally by measuring the extension of a rubber strip as a function of either
load, temperature, or both.
3.1

Tasks
Investigate the expansion of rubber experimentally. Test the theoretical predictions you have
made and measure how real rubber behaves in relation to ideal rubber. What happens to real rubber
at extremes of temperature or load?
You will need to think very carefully about the design of your experiment and how to minimise errors.
You will have access to a rubber strip, water bath, clamps, pulleys, and retort stands, a travelling
microscope, a ruler, thermometer, newton meter and a selection of weights.

Experiment: Thermal expansion coefficient of unloaded rubber

The thermal expansion coefficient is defined as,

=

1 dL
.
L dT

(8)

For most materials this is small, Tipler [3] gives values between 106 to 105 K1 for various materials from
Diamond to Copper. For non-ideal real rubber the quoted values vary widely, for example from 2.2 104
K1 [4] to 7.7 105 K1 [5]. Pellicer et al [6] derive the following result by considering the equation of
state and the 1st law,




U
2
2
= AT + 2 ,
(9)
L T

where A is a positive constant and = L1o dLo

dT is the thermal expansion coefficient of un-stretched rubber
[6]. If the rubber is un-stretched, then from Eq. 9 we can write,


U
1
,
(10)
=
3kT 2 L T


where is usually assumed to be constant and the sign of clearly depends on the sign of U
. Ideal
L
T


U
rubber is a Joules law substance ( L T = 0) so the deviation of the thermal expansion coefficient from
zero will give us some information about how ideal real rubber actually is.
Conceptually, measuring the thermal expansion coefficient of a material is easy, we simply need to measure
the length as a function of temperature. In practice, however, this can be difficult. Essentially we need
to measure changes in length of the order of just a few 100 nanometres, and one of the few ways of doing
this accurately is to use a laser interferometer. Figure 2 shows a schematic of the experimental set-up that

Figure 2: The experimental set-up.

you will use to measure the thermal expansion coefficient of rubber. The key components are those on
the optical bench. The laser (wavelength ), beam splitter and the mirrors M 3 and M 4 form a Michelson
interferometer. The purpose of Mirrors M1 and M2 is simply to adjust the height of the beam coming from
the laser. Depending on the optical components available they may not be needed.

The operation of the Michelson interferometer is relatively simple and is explained in detail in Ref. [7].
Imagine that the optical path lengths B M 3 and B M 4 are the same, then the light travelling from
B to M 3 and back to B will travel exactly the same distance as the light going from B to M 4 and back to
B. These light waves will interfere constructively at B and a bright central spot will be seen on the screen.
If the movable mirror M 4 is moved by one quarter of a wavelength each wave arriving at B will be half
a wavelength out of phase, and the central spot will change from bright to dark. If the movable mirror is
then moved by a further one quarter of a wavelength, the central spot will again be bright and each fringe
will have moved to the position previously occupied by the adjacent fringe. So, by counting the number of
fringes n that move past a fixed reference point we can accurately determine the distance L moved by the
mirror,

(11)
L = n .
2

Figure 3: Example output from the photodiode: 20 bright fringes counted in 400 seconds corresponding to a
temperature change of 4.2 K.

In Fig. 2 the heat chamber can be considered as a black box that contains the mirror, M 4, mounted
onto one end of a thin rubber bar of length 20 mm (diameter 10mm). The chamber also contains a heater
plate and two thermocouples, allowing the rubber to be heated and its temperature to be measured. The
thermocouple has been pre-calibrated between 0.1 and 0.5 V, and its temperature ( C), voltage relation is,
T (V ) = 159.2 + 592.8V

(12)

When the rubber is heated it may expand, moving the mirror M 4 and changing the interference pattern.
The number of fringes which pass a fixed reference point on the screen can be counted by eye, or by using
the photodiode and pico-Logger software. The photodiode will register a high voltage if the fringe is bright
and a low voltage if the fringe is dark (see Fig. 3). The lens is used to expand out the interference pattern so
that it can be viewed on a screen at a reasonable distance from the beam splitter (note that the beam splitter
in the lab contains a compensator plate). The purpose of the mirrors M 1 and M 2 is to give a horizontal
beam aligned at the height of the rest of the optics in the experiment. This experiment can be challenging.
It is essential to align the optics correctly and some time (and patience) should be expended optimising the
alignment.
4.1

Tasks
Set up the experiment as suggested in Fig. 2 and measure the expansion coefficient of
rubber as a function of temperature. What does the value you measure tell you about the idealness of real rubber. How much does the expansion coefficient vary as a function of temperature and
theoretically how might you expect it to vary?

As usual you should analyse and discuss the sources of error and limitations in the experiment and
think about how to minimise these.
The following hints may help when constructing a Michelson interferometer.
1. Set up the laser with the beam parallel to the surface of the optical bench.
2. Adjust the heights of M1, M2, and BS so that the beam hits the center of each when you slide each
into the beam. Mark the center of the screen E at the same height.
3. Set the optical path BS to M1 equal to BS to M2 within 1 mm or so if possible
4. Cover M2. Adjust orientation of BS so that it reflects the beam returning from M1 into the centre of
the screen.
5. Uncover M2. Note the appearance of an additional bright spot on the screen. Again, ignore the weak
spots.
6. Adjust the orientation of M2 so that the brightest spot on the screen due to the beam from M2 precisely
coincides with the brightest spot from M1. Interference often causes the brightness of the combined
spot to flicker.
7. Insert a 40x microscope objective lens (L3) between BS and the screen to make the fringes visible.

References
[1] http://prb.aps.org, see papers in the current issue and instructions for authors.
[2] I. M
uller and P. Strehlow, Rubber and Rubber Balloons: Paradigms of Thermodynamics, Springer (2004).
[3] P. A. Tipler, Physics for scientists and engineers, 4th Ed., W. H. Freeman and Company, p634.
[4] Polymer Handbook, edited by J. Bandru, E. H. Immergut, Wiley New York (1975).
[5] http://www.engineeringtoolbox.com/linear-expansion-coefficients-d 95.html
[6] J. Pellicer, J. A. Manzanares, J. Z
un
iga and P. Utrillas, J. Chem. Ed 78, 263, (2001).
[7] E. Hecht, Optics, 2nd Ed., Addison-Wesley, sect. 9.4.2.

Mervyn Roy, 2011

Using the ADC 11 picoLog Recorder

S. A. Atarah (2008)
The following are guiding steps to setting up and using the software which controls
the pico data logger to collect data. Use the following steps to set up the software.
Login to Windows
Click Start>All Programs >Pico Technology>PicoLog Recorder
On the Welcome to PicoLog for Windows screen, choose Normal
On the main window, go to File>New Settings
Choose the following settings;
Recording method
Real time continuous
Action at end of run
Stop
Restart delay
1 minute
Use multiple converters
No
The figure illustrate each stage of the configuration process.

Press OK
Choose the following settings;
Sampling interval
Maximum number of samples
Readings per sample

S.A Atarah

1s
1500 (or other suitable)
As many as possible

Press OK
Choose the following
Converter type
USB Devices:
Device

ADC-11 (USB)
ADC-11 (USB)

Serial KJLxxxx

Press OK.
This opens the window entitled ADC11/22 measurements
Press Add. This opens up the window entitled Edit ADC11 measurement
You may enter a short text for Name to describe the channel or leave as blank. In the
Channel field, enter a digit corresponding to the channel number or use default
number. Press OK. One channel has been set up.
Press Add again and repeat previous step till enough channels have been set up.
S.A Atarah

Go to File>New Data
Enter a file name for the data to be collected, then press OK. Further settings such as
data resolution can be made by clicking on Options at the stage.
To start collecting data press the red Start recording button.
Once started, the data may be viewed as a sheet or a graph. Click on the button with a
picture of (a grid) a graph on it. This will present a real time (sheet) graph of the data.
Left clicking will zoom in and right clicking will zoom out. In the top left hand corner
there is readout of the coordinates of the crosshairs. So, hovering over a point of
interest on the graph will give you the time and voltage coordinates.

S.A Atarah