Amorphous Polymers

When is a Polymer Amorphous ? Examples Why is a Polymer Amorphous ? Amorphous Polymer Properties Structure of Amorphous Polymers Long Range vs Short Range Order Shape of Polymer Chains (Random Coil Models) Experimental Confirmations (Neutron Scattering) Other Models (Non Random Coils) Dynamics of Polymer Chains: Viscosity

When is a Polymer Amorphous ?

Glassy Polymer Amorphous below Tg: PS, PMMA, Epoxy at Room Temperature Rubbery Polymer Amorphous above Tg: Crosslinked High Molar Mass Polyisoprene, Polychloroprene, Silicones, Polybutadiene at room temperature Molten Semicrystalline Polymer Crystallizable Polymer above Tm: PE (T > 140C), it-PP (T > 170C), PET (T > 270C), PEEK (T > 360C) Between Crystals in Semicrystalline Polymers (T < Tm)

Why is a Polymer Amorphous ?

Amorphous state stable above Tm Some polymers do not crystallize Why ? Crystallization kinetics too slow (next chapter) Structure is not conducive to order Tacticity defects Regio defects Branching (copolymerization)
Macromolecules, 1999

Degree of Crystallinity of Statistical Ethylene Copolymers as a Function of Branch Content

Properties of Amorphous Polymers

Below Tg

Molecular motion is very localized (vibrations and few bond rotations) Hard, Brittle and High Modulus

In the Tg Region

Onset of large-scale molecular motions (vibration and significant bond rotations) Soft, tough and lower Modulus. Properties depend on time/speed/frequency of perturbation

Rubbery Plateau Region Flow Region

Structure of Amorphous Polymers

Short-Range Order No Long-Range Order

a) liquid benzene b) glass slide; c) quartz powder d) single crystal (organic salt)

a) polybutadiene (stretched 535%); b) Silicone (stretched 540%; c) sodium metaphosphate glass fiber

Chain Size and Chain Statistics (linear polymers)

Knowing the number of repeat units of a polymer chain, can we calculate its size ? Three basic models for linear polymer chains with various levels of approximation and sophistication. Random flight or freely jointed chain model: Assume the polymer chain can be described by a random flight in three dimensions (fixed bond length & random valence angle) Freely rotating chain model: Add the constraint of fixed valence angle to the previous model Hindered rotation model: Add the constraint that the dihedral angles describing the rotation of backbone atoms around single bonds cannot be random.

Random Flight or Freely Jointed Chain Model:

(a.k.a. random walk, drunken sailor, etc..)
Question: What is the distance separating the beginning and the end points of a random walk of N steps, each of length L ? Vectorial Approach: i=N r

r r = Li
i =1

i =1 j =1 j =1 i =1 r r r 2 i= N r r r = Li Li + 2 Li L j i =1 1 i < j N
2 2 i= N j= N i =1 j =1

i =N j = N r r r 2 i= N r j =N r r = Li L j = Li L j

= NL + 2 L cos ij = NL2

( )

r2 r = NL2
mean squared end to end distance

zero

Freely Rotating Chain Model

Valence angles are identical and fixed and bonds can rotate freely around each other preserving the valence angle

r2 r

= NL fr 1 + cos

2 1 cos

Since > 90 (usually), <r2>fr > <r2>fj In the case of an all-carbon backbone = ca. 109 , cos() = -1/3

r2 r

fr

= 2 NL

Hindered Rotation Chain Model

Rotations around single bonds along the chain are not free. Hindered Rotations are due to Steric Repulsions between chemical groups in neighboring repeat units.
mean squared unperturbed end-to-end distance

r2 r

= NL 0 1 + cos 1 + cos
Steric factor, 2

1 cos 1 cos 2

Characteristic ratio

C =

r2

0 NL2

Rotational Potential

Molecular Weight Dependence of Chain Size in the Pure Melt (Theta State)

The results discussed in the previous slide apply to the case of polymer chains in the melt or in solution at the theta temperature where they have their unperturbed dimensions.

Experimental Evidence for the Random Coil Model

SANS: Small Angle Neutron Scattering Zimm Plot Radius of Gyration and Weight Average Molar Mass

Structure Property Correlations:

Chain Characteristic Ratio, Packing Length, Entanglement Molar Mass, Rubbery Plateau Modulus
Packing Length: p p can be viewed as the molecular diameter of the repeat unit in a polymer chain. p is defined as the ratio of the volume occupied by a chain divided by it mean square end to end distance.

p=
2

M < r 2 >0 N a
2

< r >0 = C nl0

Me: Entanglement Molar Mass GN0: Rubbery Plateau Modulus

0 GN =

0.8 RT Me

J. Polym. Sci. Polym. Phys. Ed. 1999, 37, 1023

Other Models of the Amorphous Phase