Chemical Structure and Polymer

Morphology
ch 3
In this chapter

To get general understanding of polymer morphology and

thermal behavior related to chemical structure

✓ Intermolecular forces
✓ Morphology, amorphous state
✓ Thermal behavior
✓ Glass transition temperature
✓ Stereochemistry
✓ Crystallinity and liquid crystallinity
✓ Chemical and physical crosslinking
 Structure-Property Relationship

Morphology

Application

Polymer Chemical Polymer

Synthesis Structure Property

Mechanical, physical, chemical property

 Molecular Weight and Intermolecular Forces
: Ultimate property of any polymer, whether as plastic, fiber, or rubber,
result from a combination of molecular weight and chemical structure.

• Intermolecular forces:
– Dispersion force
– Dipole-dipole interaction
– Hydrogen bonding
– Ionic bonding and ion-dipole interaction

* Intermolecular forces drop off rapidly with distance of separation

Morphology
: the structure, arrangement and physical form of polymer
- closely related to i) chemical structure of repeat unit, ii) polymer
chain topology, iii) higher order intra- and inter-chain organization

Solid State

Amorphous Crystalline
no order order
randomly coiled and entangled regular array of molecules
Morphology exhibit significant influence on the physical, thermal,
and mechanical properties of polymers

fringed micelle model

 Industrial Polymer

• Amorphous Polymers: individual chains are randomly coiled and

interwound with no molecular order or structure. (resemble “a bowl of
spaghetti”)

ex) PS, PMMA, PC, PVC, rubber polymers…

• Crystalline Polymers: polymer chains are arranged in highly regular

structures called crystallites.

ex) PE, i-PP, Nylon, PET(fiber), Teflon …

Crystalline polymers
Invariably do not form perfect crystalline materials
but instead are semicrystalline with both crystalline
and amorphous regions.
The crystalline phase of such polymers are
characterized by their melting temperature (Tm).

Amorphous polymers
Characterized by their glass transition temperature
(Tg), the temperature at which they transform
abruptly from the glass state (hard) to the rubbery
state (soft). This transition corresponds to the onset
of chain motion.
 Amorphous State
: Characteristics of those polymers in the solid state that, for reasons of
structure, (also kinetics), exhibit no tendency toward crystallinity.
: Also characteristics of all polymers at temperature above the melting points
(except under special circumstance where liquid crystal may form)

A. Solid amorphous state (called glassy state):

1) molecular motion is restricted to a very short range
vibration and rotation
2) above a certain temperature (Tg), segmental motion can
occur and the polymer begin to flow

B. Liquid amorphous state: viscous and flow

* Metastable amorphous state (ex. vitrified PET )

 Glass Transition Temperature (Tg)
: Defined as temperature or narrow range of temperatures
where an amorphous glassy state changes to rubbery state.
(second-order transition)

At Tg upon heating:
Long range segmental motion begins
(20-50 atoms in polymer backbone move cooperatively)

Property change at Tg:

specific volume increase (by dilatometry)
modulus (or stiffness) decrease (by mechanical measurement)
heat capacity change (by calorimetry)

Tg is characteristic of a particular polymer,

related to polymer properties and processing..
Factors determining Tg : general five factors

• Free volume (Vf = V – Vo)

• Polar interaction between the molecules
• Torsional mobility of the chains
• Chain stiffness
• Molecular weight

• Crosslinking (reduce segment mobility)

Glass Transition Temperature of Selected Vinyl Polymers
Glass Transition Temperature of Representative vinyl Polymers
Glass Transition Temperature of Representative Non-vinyl Polymers
Exercise #7. Which polymer is expected to exhibit higher Tg?

a
a
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N
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 Stereochemistry
: important structural parameter, lead to crystallinity

Tacticity is the relative stereochemistry of adjacent chiral

centers within a macromolecule.

random configuration Atactic or heterotactic

* Stereoregular polymers (ex. isotactic polypropylene, i-PP)

Isotactic polypropylene chain has ordered placement of the CH3
groups. This type of arrangement lead to close molecular-chain
packing and crystallinity

Syndiotactic polypropylene, the CH3 groups are arrange regularly

alternating the CH3 molecules on either side of backbone of the
chain, which lead toward a tougher, more dense crystalline
structure.
Atactic polypropylene is formed that has a random placement of
the CH3 groups. This random placement prevents chain packing and
a noncrystalline polymer is formed. This polymer is soft, weak and
less cloudy than the more crystalline isotactic and syndiotactic forms.

Isotactic PP: possess versatile uses such as fabrics for carpets,

automobile parts, battery casings, medicine bottles
Syndiotactic PP: newly developed, applications are emerging.
Atactic PP: soft matter, not very useful.
 Try to
Draw the structure of atactic polystyrene and
syndiotactic PMMA
 Crystallinity and Crystalline Polymer

1. Requirements for crystallization

a. Regularity of molecular structure with little or no branching
(tactic polymer)
b. Intermolecular forces (highly polar group, e.g. amide group)

2. Inducing crystallinity
a. Cooling of molten polymer (or evaporation of polymer solution)
b. Annealing: heating at a specified temperature in inert atmosphere
c. Drawing: stretching a polymer sample at temperature above Tg,

3. Properties of crystalline polymers, in general

a. Tougher b. Stiffer c. Opaque : light scattering
d. More resistant to solvents e. Higher density

Crystallinity is extremely important for mechanical property .

The Crystalline State

Spherulites
Lamellae
of folded chains
Crystalline-Melting Temperature (Tm)

First-order transition temperature

At the equilibrium crystalline melting point (Tm)

ΔGm = 0, so Tm = ΔHm / ΔSm

PET

Solid state amorphous

(PET bottle)

Rapid cooling

vitrification devitrification
Liquid state amorphous
(molten PET)

Slow cooling
(Crystallization)

Crystalline state
(polyester fiber)

AboveTm
Above Tm Below Tg
BlowTg
 Liquid Crystallinity
a. Intermediate between liquid and crystalline solid
1) have intermediate orientational and positional order
2) ordered region is called Mesophase
3) occur bet. conventional mp and true isotropic solution
b. Unique properties of LCs: orientation under electric and magnetic field,
color or opacity change upon temperature
c. Lyotropic and thermotropic / Nematic, semectic, cholesteric, etc
d. Importance in polymer material property
1) lower viscosity
2) maintain ordered configuration in the solid state
ex 1. Thermotropic LC Copolyester (Vectra®)

ex 2. Aramid (Kevlar®) is a commercially available Lyotropic LCP

 Thermal Behavior of
Amorphous and Crystalline Polymers
 Crosslinking
A. Chemical crosslinking (curing)
1) linking the polymer chains together through covalent bonds
to form a network.
2) crosslinked polymer is not soluble but swell by any solvent.
3) do not melt but decompose at a certain high temperature.

* Method of chemical crosslinking:

1) crosslinking during polymerization by using
polyfunctional monomer or crosslinking agent.
2) stepwise crosslinking.
1st step : to make linear or branched polymer.
2nd step : crosslinking step to make network from free polymer.

B. Physical crosslinking
1) thermally labile crosslinks (ionic crosslink - ionomer)
2) introduce crystalline domain
3) block copolymers (ABA type, thermoplastic elastomer)
 Thermoplastic Elastomer (TPE)

SBS

See Table 3.6 (text) Commercially Important TPEs