Chapter 1.

Macromolecular statistics and chain dimensions

OBJECTIV: to study and understand the spatial shapes of polymer
chains in solutions and at the molten state, and the way the
shape is altered by application of flow (shear and
elongational)

Lecture 1/30
1. Revision of concepts/new concepts:
Interaction potential energy between chain segments.
Types of molecular structures: linear, branched and crosslinked
chains.
Chemical regularity: homopolymers and copolymers.
Stereochemical regularity: isotactic, syndotactic and atactic
configurations.

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1. Revision of concepts/ new concepts

J. A. Martins, DEP, Univ. Minho, 2007/2008.

Exerccio 1.
It also means that you need to study to succeed in this discipline.

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J. A. Martins, DEP, Univ. Minho, 2007/2008.

Solution
6
6
a) dW(r)/dr = 0 r = re = 2 B A

b) W(r) = 0 at

r06 = B A

W (re ) = A 2 re6

r06 re6 = 1 2 re ro = 1.12

c) F = dW (r ) dr Fmax at rF6 = 26 B 7 A

rF ro = 1.24 and rF re = 1.11

d)
re

e) F = -1.89 x 10-10 N
(attractive)

rF

0
r0

W(r)
NOTE the definition of FORCE
as MINUS the derivative of the
interaction energy.

F(r)=-d W(r)/dr

Minimum interaction energy

Maximum force
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J. A. Martins, DEP, Univ. Minho, 2007/2008.

A = 10-77 J m6
B = 10-134 J m12

Note the values for the distance at

the equilibrium interaction energy
3.5
and maximum force
4 . For forces above this value
(189 pN) rupture occurs.
These are typical values for the
interaction forces between polymer
chains. For aligned polymer
chains, the force increases
significantly due to the increase of
interaction potential energy with the
length of aligned segments.

Bond Type
dispersion
hydrophobic
H-bonding
ion-ion
covalent

Interaction Distance ()
3.5
3.5
3
2.5
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The relatively higher stresses for

yield of polymers may be crudely
estimated from the interaction
potential between them and the
average dimension of the aligned
regions there existing (lamellae or
oriented chains).
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J. A. Martins, DEP, Univ. Minho, 2007/2008.

STRONG AND WEAK BONDS

Force

Modulus of ELASTICITY =
STRESS (or force per unit area) / strain
dF/da

( dF / dr ) r = r0

distance
WEAK bond

( dF / dr ) r = r0

Strong bonds dF/da high High

modulus

STRONG Bond

The strength of a bond (or physical interaction) depends of the DEPTH OF POTENTIAL
WELL.
STRONG bonds have deep potential wells, which results in large maximum forces
The depth of potential well is also called BINDING ENERGY or BOND DISSOCIATION
ENERGY
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J. A. Martins, DEP, Univ. Minho, 2007/2008.

The bonds or intereactions responsible for joining the atoms together are of two types:

SE
CO
ND

AR
Y

PR I
MA

RY

1. PRIMARY, the strongest,

2. SECONDARY, the weakest.

bond / interaction

Example

Order of magnitude
(kJ/mol) ]

Covalent
Ionic

H-H; C-C
Na+ Cl-

180 - 800
500 - 1000

Metalic

Mg, Cu, Al

180 - 800

Hydrogen bonding

H2O ... H2O

4 - 40

Van der Waals

CH ... CH3

0.4 - 4

] The bonding energy depends on the separation distance, charge, dipole

moment, polarizability and dielectric constant of the medium.
Bond versus physical interaction: In a CHEMICAL BOND, such as COVALENT BOND,
there is sharing of electrons and directionality of the bond. Other physical binding forces, that
can be strongest than a covalent bond, are better classified as PHYSICAL INTERACTIONS
or PHYSICAL BONDS.
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J. A. Martins, DEP, Univ. Minho, 2007/2008.

Thermal energy at T= 300 K = 2.494 kJ/mol.

The state of a pure substance or compound at room temperature depends on PRESSURE
and TEMPERATURE.
At atmosferic pressure its state is determined by the ratio of the binding energy of

its bonds and its kinetic energy at a specific temperature.

>> 1 SOLID

~1 LIQUID

<< 1

GAS

Their are FOUR states of matter. Besides the indicated, there is still the PLASMA state.
At this state atmos are ionized.
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J. A. Martins, DEP, Univ. Minho, 2007/2008.

Changing temperature and pressure, any

substance may exist as solid, liquid or gas.
The physical states are determined by
attraction forces.
Primary and secondary bonds are
responsible for phase transitions.

PHASE Homogeneous part of a system in

conatct with other parts of the same
system, separated by a boundary. At a
molecular scale the boundary is not well
defined. In the vaporization of water, or
sublimation of dry ice, the boundary is
diffuse. In liquid-solid transitions the
boundary may be well defined, BUT only at
low supercoolings and short time scale.
PHASE TRANSITIONS may be of 1st or 2nd
order.
FIRST order phase transitions require transfer of heat to break PRIMARY or
SECONDARY bonds THE LATENT HEAT.
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J. A. Martins, DEP, Univ. Minho, 2007/2008.

Condensed states: LIQUIDS AND SOLIDS

SOLIDS
LIQUIDS
Molecules are joined together by
attraction forces.
The free space between molecules is
reduced difficult compressibility.
Their volume is well defined.
Free relative movement of molecules.
A liquid fits to the shape of its container.

Molecules are joined together

rigidly and vibrate around a fixed
point.
Are less compressible than
liquids.
Solids are generally more dense
than liquids. Exception: water.
Have shape and volume defined.

GASES
1
Free translational movement E k = 3 * RT

No form or volume defined. Fits to the shape of its container. Very

compressible.
Low density.
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J. A. Martins, DEP, Univ. Minho, 2007/2008.

How to explain the condensation of a gas?

Thermal agitation decreases with lowering of temperature.
The gas kinetic energy is lower than the energy of INTERMOLECULAR interactions.
As a result of these forces, gas molecules aggregate and the gas changes to a liquid
CONDENSATION.
Ebullition and melting temperatures increase with the intensity of INTERMOLECULAR
interactions.

Why INTERMOLECULAR interactions are important?

They determine most properties of SOFT MATTER (structured fluids), and explain:
the interactions between polymers and solvents
the reason why most polymers are immiscible
why oil does not mix with water
why the drop of any liquid has a spherical shape
why a drop of water does not spread onto a plastic surface
why adhesives bind to a variety of surfaces
the low friction coefficient shown by some polymers
the interactions between colloidal particles (ex. paints).
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J. A. Martins, DEP, Univ. Minho, 2007/2008.

1. Revision of concepts/ new concepts

Interaction potential energy between two parallel chain segments

The interaction potential energy considering only the atractive term
of Lennard-Jones potential energy is
3 CL

W =

8 r

2 5

A= 2 2C

A Hamaker constant
the number density of molecules in each chain
- the effective bond lenght, l cos(val.angle / 2)
r the equilibrium separation distance between the chain axis of two
chain segements (van der Waals diameter of the chain) sum of
the effective bond length along the transverse chain direction and
the closest separation distance between two hydrogen atoms
(2.24 )
2

Atotal = A =0 + A >0
Entropic term
(Keesom e Debye)

(
(

)
)

2
o
3h e n 2 no
3
+
= k BT

32
4

+
16 2 n 2 + no 2
o

Dispersion forces contribution (London)

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1. Revision of concepts/ new concepts

J. A. Martins, DEP, Univ. Minho, 2007/2008.

Application to polypropylene
9.96 x 1028 m-3 (ratio between the number of atoms per monomer
and the monomer van der Waals volume).
r = 3.74
= 1.27
(CHECK THESE THREE VALUES. WRITE THE BASE POLYMER UNIT.
C-C BOND LENGTH = 1.54 , VALENCE ANGLE 110 ).

e 3.0 x 1015 Hz Maximum absorption electronic frequency at UV

T = 400 K (typical crystallization temperature of iPP)
= 2.2 , n = 1.5 and h Planck constant A = 5.68 x 10-20 J

W-33.4*L (J/mol) with L in

For a typical thickness of a lamellae in a semicrytalline polymer, L = 100 ,
W = 3.34 kJ/mol.
Thermal energy at room temperature (T = 300 K) 2.5 kJ/mol
NOTE how weak are the interactions holding on the crystalline part in
semicrystalline polymers. NOTE also the linear increase of interaction potential
energy with L. Try to imagine the magnitude of these interactions in polymer fibers
and stretched melts.
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J. A. Martins, DEP, Univ. Minho, 2007/2008.

1. Revision of concepts/ new concepts

Revision of concepts: A. Types of polymer chains

Applications:
molecular switches,
Molecular electronics

Applications:
Drug delivery,
Photonics,
Artificial
photosynthesis
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1. Revision of concepts/ new concepts

J. A. Martins, DEP, Univ. Minho, 2007/2008.

Linear, branched and crosslinked polymer chains may also be classified according
to their chemical regularity and tacticily.

Types of chemical regularity

Homopolymer

Random
copolymer
Alternating
copolymer
Block
copolymer
Graft
copolymer

Copolymer: contains more than one species

of monomer
Terpolymer: contains three different
monomers
Example:
Styrene-methyl methacrylate copolymer
Poly[styrene-co-methyl methacrylate]
Poly[styrene-alt-methyl methacrylate]
Polystyrene-block-methyl methacrylate
Poly[styrene-graft-methyl methacrylate

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J. A. Martins, DEP, Univ. Minho, 2007/2008.

1. Revision of concepts/ new concepts

Types of stereochemical regularity

A. Isotactic polymer: Side groups all at the same side of the chain

B. Syndiotactic polymer: Side groups alternating at the left and rig-hand

side of the chain

C. Atactic polymer: Side groups distributed randomly

A and B crystallize if they have also chemical regularity: homopolymers and

block copolymers.
C never crystallizes. A and B without chemical regularity (ex. Random
copolymers) never crystallize also.
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J. A. Martins, DEP, Univ. Minho, 2007/2008.