MS 6503: Polymer Physics Session A

1. Introduction to Polymers
Polymeric materials include the following substances of both, natural and synthetic
origin: plastics, rubbers, foams, films, fibres, wood, cotton, wool, proteins, coatings,
paints, adhesives, sealants, and the like.
The division of polymeric materials into plastics, rubbers, paints, etc., is historical,
based on their industrial origins. All these substances are polymeric, and can be studied
by the same approach and understood by the same science. It is important to stress that
one should use the term polymeric materials in all situations in which other types of
materials are referred to as ceramic materials, or metallic materials, or electronic
materials. This is the correct way to distinguish between the different types of materials
on the basis of our knowledge of materials science. However, when referring to specific
polymeric materials in technological or popular terms, then we may use such terms as
plastics, textiles, rubbers, FRP (fibre reinforced plastics), etc. These names should be
used in situations in which other materials would be described as concrete, steel,
aluminium alloys, timber, etc.
The essential feature of the polymeric state (as opposed to metals or ceramics) is the
existence of the macromolecules. The atoms in the centre of the polymer chain form the
backbone of the macromolecule. The atoms or groups of atoms on the side of the chain
are called side groups or branches, depending on their number and arrangement.
Polymeric materials are as old as humanity, and yet as new as this century. Walls of
clay with additions of straw have been made for thousands of years. Cellulose fibres from
papyrus had served since ancient times as a medium for recording human thoughts and
events. Animal tendons, wood and silk, bonded together with a natural polymeric
adhesive, were used for making boats, bows and arrows, and other implements.

2. Polymer chemistry
Addition polymerisation (chain growth – typically homopolymers)
(i) dissociation, (ii) initiation, (iii) chain reaction, (iv) termination
Condensation polymerisation (step growth – typically copolymers and networks)
(i) initiation, (ii) gelation, (iii) vitrification

The end products of polymerisations are molecular chains; if the degree of

polymerisation is less than approximately 1000 then the molecules are called oligomers,
otherwise they are polymers.
The word polymer was derived from the Greek language by Berzelius; πολυ -
meaning many, and µερησ - meaning a part, i.e. a molecule of many parts (Jons Jacob
Berzelius, 1779-1848, Swedish chemist). Many identical chemical groups, the mers, are
joined together by strong covalent bonds (in a chain-like structure) to form a
macromolecule. The strength of these covalent bonds guarantees the integrity of the
macromolecular chain up to high temperatures. However, in the presence of oxygen, and
due to the chemical reactivity of the side groups, the decomposition temperatures of most
polymers lie in the range of 300˚ - 500˚C.
Modern polymer science has developed only in the last century. One of the major
landmarks occurred in the 1920’s when Staudinger was able to show convincingly that
these substances were made of long chains and not colloidal particles as was though at the
time [Hermann Staudinger, German polymer scientists, 1881-1965].

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 MS 6503: Polymer Physics Session A

3. Common methods used for characterisation of polymers

a. Calorimetry (Tm, Tg, cp, Δh)
b. IR spectroscopy (identification, quantitative molecular groups)
c. NMR spectroscopy (molecular dynamics)
d. GPC (molecular weight distribution)
e. OM (morphology of crystalline structure)
f. XRD (crystal structure, degree of crystallinity)
g. Dilatometry (kinetics of transformations)
h. Rheometry (shear and extensional viscosity)
i. Mechanical testing (elastic modulus, tensile strength)

4. Levels of simplification of polymer chains

level 0 full chemistry representation of polymer chain

level 1 computer simulations, consistent valency force-field

atom sizes = valency diameters

level 2 bead (unified atom = combined mass) and spring model

with covalent and rotational potentials

level 3 freely jointed link chain model (random walks)

5. Properties and behaviour of single polymer chain

Bonds and interatomic forces in a molecular chain:
Interatomic forces have electromagnetic origin:
• When atoms with closed shells of electrons overlap, the interaction causes
repulsion.
• Valence interactions of open shell atoms cause attraction with the formation of a
chemical bond.
• At larger separations further electrostatic interactions may occur, resulting in
electrostatic, induction or dispersion effects [“The forces between molecules” by
M. Rigby, E. Smith, W. Wakeham and G. Maitland, Clarendon Press, Oxford
1986].
The interatomic force, F(r), and the bond stiffness, S(r), are related to the bond potential
energy, U(r). All three quantities are strongly dependent on the distance (separation)
between the atoms, r. In general, the relationships are given by:
dU(r) d 2U(r)
F(r) = " , and the bond stiffness: S(r) = " (1)
dr dr 2
The potential energy of interatomic bonds is equal to the work done in bringing the atoms
together from infinite separation to a distance r. It can be represented as:
! "
!
U(r) = # F(r)dr = $ %(r /& ) , (2)
r

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 MS 6503: Polymer Physics Session A

where: " is a parameter related to the strength of the bond (depth of potential well), σ is a
parameter representing an equilibrium distance between the atoms, r is the actual distance
between the atoms, and " is called a shape function of the curve of U(r) versus r.
! To a first approximation the potential energy is independent of temperature.
For two different atoms, A and B, the combining rules are:
!
1
" AB = (" AA + " BB ) (Lorentz-Berthelot rule) (3)
2
1 1# 1 1 &
= % + ( (harmonic mean rule) (4)
" AB 2 $" AA "BB '
!
Note that the stiffness of interatomic bonds is measured indirectly in infra-red (IR)
! spectroscopy. An absorption band in an IR spectrum occurs at a frequency given by:
1 $ 1 1 '
"= k& + ), where k = S (5)
2# % m A mB (
Therefore, measuring the frequency of the absorption band, and knowing the masses of
the vibrating atoms allows calculation of the stiffness of the bond
!
The potential energy due to interatomic interactions in a polymer can be represented by
the consistent valency forcefield (CVFF):

Figure 1. The range of interatomic forces considered in computer simulations of polymers.

The first four terms describe the potential energy required to: (i) stretch bonds, (ii) bend
covalent angles, (iii) rotate torsion angles, (iv) distort planar atoms out of plane.
The next five terms are cross-terms that account for the interactions between the four
types of forces listed above.
The last term represents the non-bonded interactions between neighbouring chain
segments (or other chians) that come in contact with each other.

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 MS 6503: Polymer Physics Session A

6. Physics of polymer chains

United atom and bead and spring models
Physical approach to polymers is to simplify the structure of the molecular chains in
order to discover properties common to all polymers. The first simplification is to
represent the mer units of the chain as a beads (spheres). For polyethylene each bead
represents CH2 atoms, for polystyrene each bead represents the CH2CHC6H5 group of
atoms, and the like for other polymers. The second simplification is to represent the bonds
between the beads by elastic springs (or rigid links). With these simplifications all
polymer chains look the same.

Figure 2. Representation of a segment of a united

atom chain, consisting of beads connected by fixed
length links (no extension or contraction allowed), but
rotation around the links is free (three possible
positions in the i+1 link are shown). The angle
bewteen consequtive steps (i-1 to i, i to i+1, etc) may
be the same or may vary.

Motion of beads in the chains

At a temperature, T, each bead in the chain possesses thermal energy of the order, kBT (kB
is the Boltzmann constant) in the form of thermal vibrations, which, to a good
approximation can be described as harmonic sinusoidal oscillations. In addition, the
motion of each bead is further affected by the random impulses from other surrounding
chains. Together, the motion of each bead can be described by the Langevin equation:
"2 " "
mi r (t) = #$
2 i
ri (t) # U(r) + f Ln (t) , (7)
"t "t "ri
where: m [kg] is the mass of the bead, ri(t) [m] is the time dependent position vector of
the bead, ζ [Ns/m] is the friction coefficient associated with the motion of the bead, U(r)
! [J] is the potential energy field surrounding the bead, and fLn(t) [N] is the stochastic force
imposed on the i’th bead by the surrounding chains. In molecular dynamics simulations,
for times t >> m/ζ ≈ 10-13 s-1, the acceleration term can be neglected, and equation (7)
reduces to:
# #
" ri (t) = $ U(r) + f Ln (t) (8)
#t #ri
Equation (8) shows that the instantaneous velocity at time t of the i’th bead is governed by
the potential energy surrounding it and the stochastic impact force acting on in it. The
stochastic impact force acts on the beads at random.
!
Then, a fundamental property of the chain, which is a consequence of its flexibility and
the thermal motions, is the random coil-like shape of the chain. We use mathematics of
random walks to describe this property.

The properties of random walks

Consider a random walk of equal steps in space. Let the length of the step a be a
vector, ai. After n number of steps, the end-to-end vector distance of the walk is given by:
r n
r = "ai (9)
i =1
The square end-to-end distance is equal to:

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 MS 6503: Polymer Physics Session A

n
r nr n
r n#1 n
rr
r 2 = " ri " r j = " ri2 + 2 " " ri r j (10)
i=1 j=1 i=1 i=1 j=i+1
The important question is “what is the end-to-end distance of the random walk for a large
number of walks?”. The answer is given by the statistical quantity known as the mean
square end-to-end distance:
!
n n%1 n
2 r2 rr
"r # = $ " ri # + 2 $ $ " ri r j # , (11)
i=1 i=1 j=i+1
where the 〈〉 brackets indicate statistical average. The first term amounts simply to na2,
and the second term is equal to na2〈cosΘij〉, where Θij is the angle between two adjacent
! step vectors. If the orientation of the steps is completely random and uncorrelated – so
called freely jointed chain, then 〈cosΘij〉 = 0, and equation (11) becomes:
1
"r 2 # = na 2 , and therefore: "r 2 # 2 = a n (12)

The second expression gives the same result as equation (9) for a single walk.
! !

Figure 3. Far right, the geometry of links and angles of a link chain.

If the angle between each step, Θ, is the same for all steps,
then the calculations give:
&1+ $ )
"r 2 # = na 2 ( , where α = cos (180°– Θ) (13)
'1% $ +*
If Θ = 90˚, then α = 0, and 〈r2〉 = na2.
Finally, if the step angle is fixed, and the rotational angle is φ,
! then:
&1+ $ ) &1+ "cos , # )
"r 2 # = na 2 ( ( + (14)
'1% $ +* '1% "cos , # *

Averaging over the rotation angles requires statistical knowledge of the frequency of the
! rotational states (statistical partition function). We can use the rotational partition
function, zg = 1 + wg, with wg = exp(-Eg/kBT). Given this, equation (14) becomes
[“Polymer Physics”, U.W. Gedde, Chapman & Hall 1995]:
&1+ $ ) &2 + w g )
"r 2 # = na 2 ( ( + (15)
'1% $ +* ' 3 *

The following important observations can be made on the basis of these relationships:
a. The mean square root end-to-end distance of the walk, "r 2 # 1 / 2 , is proportional to
!
the square root of the number of steps, i.e., the number of beads minus one (see
equation (12)).
b. The most probable square root end-to-end distance, counted over many chains, is
!
"r 2 # 1 / 2 = a√n.

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 MS 6503: Polymer Physics Session A

c. If the angle between the steps is fixed, and if Θ > 90°, then 0 < cos (180°– Θ) < 1,
and it follows from equation (13) that the mean square root end-to-end distance is
increased in comparison to the random angle walk. An angle of Θ < 90°, never
occurs in polymers.
d. If the rotational angle, φ, between i and i+2 step, is 120° (typical for many
polymers), and it is assigned according to a statistical rule, then mean square root
end-to-end distance is increased again as compared to the previous case. If the rule
is given by the partition function, zg, then it is also temperature dependent. This is
an important observation as it tells us that the size of the random walk (and
consequently the random coil size of the real chain) will depend on temperature. In
general, the mean square root end-to-end distance will increase as the temperature
is lowered.

Statistic of random walks

It should be noted that every time a random walk is made, the result is different. So the
important question should be asked “what is the distribution of the most probable end-to-
end distance of a large number of random walks?” The solution to this problem was given
by Kuhn (1934,1936) and by Guth and Mark (1934) as follows:
b3
p(x, y,z)dxdydz = 3 2 exp{#b 2 (x 2 + y 2 + z 2 )}dxdydz (16)
"
where b2 = (3/2)na2. Equation (16) gives the probability that the components of the vector
representing the end-to-end distance shall lie within the intervals x + dx, y + dy, z + dz,
respectively. Its form is that of the Gaussian error function, and therefore this solution is
!
known as the Gaussian random walk [Johann Karl Friedrich Gauss, 1777-1855, German
mathematician].

Figure 4. On the left, a random coil chain, with one end positioned at the origin of the frame of
reference (A), and the other end at position (B). The statistics of random walks (chains) predicts
the probability of finding the mass of the chain in a small element of volume at position P(x,y,z),
(see eqn (16)). On the right, a plot of this probability showing that it is maximum at the origin, and
decreases exponentially moving away from the origin.

We observe that an atom diffusing through a solid performs random uncorrelated walk;
the equations given above are also used to predict the diffusion distance, as:

Δr = a√n = D√t,

where D is the diffusion coefficient, and t is time.

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 MS 6503: Polymer Physics Session A

Since r2 = x2 + y2 + z2, then the probability for the end-to-end vector being of magnitude
lying in the range, (r, r + dr), or equivalently, of lying in a shell of radius r and thickness
dr, is given by:
4b 3
(
Pn (r)dr = 4 "r 2 p(r)dr = 1 2 r 2 exp #b 2 r 2 dr
"
) (17)

This function has a value of 0 at r = 0, increases to a maximum at rb = 1/b, and then

decreases to zero as r increases as shown in Figure 5.
!
Figure 5. A shell of
thickness dr with an end of
the random walk (chain),
and far right a plot of the
function in equation (17).

Figure 6. A rifle-shooting target with holes. The

holes are produced by aiming for the centre.
Random effects cause a distribution of the holes
around the centre. It is a 2-dimensional
analogue of the random 3-dimensional walk
problem. The centre of the target is equivalent
to the centre of the frame of reference. The
circles in the target create rings of equal
thickness, equivalent to the shells of the
corresponding sphere. The holes correspond to
the ends of the chains.

Count the number of holes (points) per ring on the target to find that it starts with a value
of 10, increases to a maximum of 19 at the 3rd ring, and then decreases again. The highest
density of dots (number/area) is at the centre, this calculations corresponds to the function
in equation (16) and Figure 4. The largest number of dots in a ring is at 3rd ring, this
calculation corresponds to the function P(r) in equation (17) and Figure 5.

The mean square value of r is calculated as follows by standard mathematical approach:

$
2 % 0 rP(r)dr
"r # = $
= na 2 , (18)
% 0 P(r)
which gives the same result as equation (12).

The functions P(r) and p(x,y,z) are also identical in form to the corresponding Maxwell
!
distribution functions representing the distribution of velocities among the molecules of a
gas. From the mathematical point of view the two problems are entirely analogous, being
concerned with the random addition of vectors.

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 MS 6503: Polymer Physics Session A

Equivalent random chain and coarse-graining

It may be shown quite generally that the statistical distribution of end-to-end distances for
any chain, whatever its geometrical (or chemical) structure, reduces to the Gaussian form
if the number of rotatable links is sufficiently large. This is true even when the rotation
about single bonds is not completely free but is restricted by energy barriers or other
hindering effects (see equations (13) to (15)). The effect of the structure of the chain on its
statistical properties is represented by the numerical value of the parameter b in equations
(16) and (17). For real chains the value of the statistical length b need not be the
monomer, but can include larger segment of the chain. It is always possible to find a
corresponding randomly jointed chain (of equal size links) which will have the same
Gaussian statistical properties as the real chain. To determine the number of links and the
length of the link in the equivalent random chain, let us assume that the actual real
macromolecule, when fully extended but without distortion of the bond lengths or valency
angles, has the so-called contour length, Lr, and that its mean square length is 〈rr2〉. Let Lm
and 〈rm2〉 be the corresponding values for the equivalent mathematical chain. If the mean
square lengths are to be the same, then:
rr2 = rm2 , where rm2 = n m am
2
(19)
and if both are to have the same extended chain length, then:
Lr = Lm , where Lm = n m am (20)
! The two simultaneous equations lead to the following solutions for the real (actual) chain:
n m = L2r /"rr2 #, and Lm = "rr2 # /Lr (21)
!
For example, for polymethylene we find from equation (13), assuming Θ = 110°.
Assuming equal distribution between trans and gauche bonds (trans, +gauche, –gauche),
! then the mean square end-to-end distance, and the fully extended length (planar zig-zag)
are:
1 2
"rr2 # $ 2n r ar2 and
Lr = n r ar cos % = n r ar (22)
2 3
Substitution of these values into equations (21) gives the equivalent mathematical chain
parameters:
! 1
nm = nr and Lm = 6Lr " 2.45Lr (23)
3
Therefore, the polymethylene chain may be replaced (at simplification level 3) by a
randomly jointed chain with one-third the number of monomers, and its statistical
! equivalent link length will be approximately 2.45 times the length between the monomers.
It follows that one random link is equivalent to 3 C–C bonds.
The quantity, Lm, of equation (21) is called Kuhn length, and in other texts may it be
denoted lK. Flory [Paul John Flory, 1910-1985, Nobel prize in chemistry in 1974, Stanford
University, California] later introduced a different quantity characterising real
macromolecular chains, called the characteristic ratio:
C" = #rr2 $ nam
2
(24)
The value of this characteristic ratio indicates the actual expansion of the size of the
macromolecular coil compared to its ideal random walk representation. It includes the
! effects of the valency and rotational angles, as well as higher order effects (excluded
volume). It is also temperature dependent, since the dynamics of the chain (i.e. its
conformations) will change with temperature.

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