Molecular Shape (or Conformation)

Chain bending and twisting are possible by rotation of carbon atoms around their chain bonds Not necessary to break chain bonds to alter molecular shape

Molecular Structures for Polymers

Linear Polymers - Mer units are joined together end to end - Polyethylene, polystyrene etc
secondary bonding

Branched Polymers -Side branches are connected to main ones - Lowering density Cross linked Polymeres - Adjacent linear chains are joined to one another at various positions by covalent
bonds

Network Polymers - polymerization of monomers having two or more functional groups -may be made by cross-linking the polymers

Molecular Configurations for Polymers

Configurations to change must break bonds

Isomerism Mmolecules with the same chemical formula and often with the same kinds of bonds between atoms, but in which the atoms are arranged differently

Propanol (C3H8O) is an example

Propan-1-ol (n-propyl alcohol) and Propan-2-ol (isopropyl alcohol)

Molecular Configurations for Polymers

Stereo Isomers Bond structure is the same but the geometrical positioning of atoms and functional groups in space differs
H C C H R H H H C C H R or H R C C H H

Stereoisomers are mirror images cant superimpose without breaking a bond

A C B E E

A C

B
4

mirror plane

Tacticity
Tacticity stereoregularity or spatial arrangement of R units along chain isotactic all R groups on syndiotactic R groups same side of chain alternate sides
H H H H H H H H C C C C C C C C H R H R H R H R H H H R H H H R C C C C C C C C H R H H H R H H

Tacticity (cont.)
atactic R groups randomly positioned
H H H H H R H H C C C C C C C C H R H R H H H R

cis/trans Isomerism

CH3 C C CH2

H CH2

CH3 C C CH2

CH2 H

cis
cis-isoprene (natural rubber) H atom and CH3 group on same side of chain

trans
trans-isoprene (gutta percha) H atom and CH3 group on opposite sides of chain

VMSE: Stereo and Geometrical Isomers

Manipulate and rotate polymer structures in 3-dimensions

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Copolymers
two or more monomers polymerized together random A and B randomly positioned along chain alternating A and B alternate in polymer chain block large blocks of A units alternate with large blocks of B units graft chains of B units grafted onto A backbone A B
random

Adapted from Fig. 4.9, Callister & Rethwisch 4e.

alternating

block

graft
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Sketch the repeat structure of Poly(Styrene-butadine) alternate polymer

Several Repeat Units in Rubbers

Thermoplastic and Thermosetting Polymers

Thermoplastic Polymers Becomes soft and formable when heated Hardened when cooled significantly below their softening point reversible process Readily recycled Produced in one step and then made into products in a subsequent process Thermosetting Polymers Do not soften upon heating cannot be shaped or formed to any great extent Produced and formed in the same step

Crystallinity in Polymers

Adapted from Fig. 4.10, Callister & Rethwisch 4e.

Ordered atomic arrangements involving molecular chains Crystal structures in terms of unit cells Example shown polyethylene unit cell

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Polymer Crystallinity

Crystalline regions thin platelets with chain folds at faces (Lamellae) Chain folded structure

10 nm

Chain-folded model
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Polymer Crystallinity (cont.)

Polymers rarely 100% crystalline

Difficult for all regions of all chains to become aligned crystalline

region

Degree of crystallinity

expressed as % crystallinity.
-- Some physical properties depend on % crystallinity. -- Heat treating causes crystalline regions to grow and % crystallinity to increase.

amorphous region
Adapted from Fig. 14.11, Callister 6e. (Fig. 14.11 is from H.W. Hayden, W.G. Moffatt, and J. Wulff, The Structure and Properties of Materials, Vol. III, Mechanical Behavior, John Wiley and Sons, Inc., 1965.)

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Polymer Crystallinity

Packing of molecular chains so as to produce an ordered array Much more complex than metals / ceramics

Not just atomic or molecular arrangements, rather molecular chains involved

c ( s a ) %crystallinity *100 s (c a )

s is the density of a specimen for which % crystallinity is to be determined a is the density of the totally amorphous polymer c is the density of the totally crystalline polymer

Example