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Structures of Polymers
ISSUES TO ADDRESS...
What are the general structural and chemical
characteristics of polymer molecules?
What are some of the common polymeric
materials, and how do they differ chemically?
How is the crystalline state in polymers different
from that in metals and ceramics ?
Chapter 5 - 1
What is a Polymer?
Poly mer
many repeat unit
Chapter 5 - 2
Ancient Polymers
Originally natural polymers were used
Wood Rubber
Cotton Wool
Leather Silk
Chapter 5 - 3
Polymer Composition
Most polymers are hydrocarbons
i.e., made up of H and C
Saturated hydrocarbons
Each carbon singly bonded to four other atoms
Example:
Ethane, C2H6
H H
H
C C
H H
H
Chapter 5 - 4
Chapter 5 - 5
Unsaturated Hydrocarbons
Double & triple bonds somewhat unstable
can form new bonds
Double bond found in ethylene or ethene - C2H4
H H
C C
H H
H C C H
Chapter 5 - 6
Isomerism
Isomerism
two compounds with same chemical formula can
have quite different structures
for example: C8H18
normal-octane
H H H H H H H H
H C C C C C C C C H = H3C CH2 CH2 CH2 CH2 CH2 CH2 CH3
H H H H H H H H
H3C ( CH2 ) CH3
6
2,4-dimethylhexane
CH3
H3C CH CH2 CH CH3
CH2
CH3
Chapter 5 - 7
Polymerization and
Polymer Chemistry
Free radical polymerization
H H H H
R + C C R C C initiation
H H H H
free radical monomer
(ethylene)
H H H H H H H H
R C C + C C R C C C C propagation
propagation
H H H H H H H H
dimer
Initiator: example - benzoyl peroxide
H H H
C O O C 2 C O =2R
H H H
Chapter 5 - 8
Chemistry and Structure of
Polyethylene
Adapted from Fig.
5.1, Callister &
Rethwisch 9e.
Chapter 5 - 9
Bulk or Commodity Polymers
Chapter 5 - 10
Bulk or Commodity Polymers (cont)
Chapter 5 - 11
Bulk or Commodity Polymers (cont)
Chapter 5 - 12
VMSE: Polymer Repeat Unit Structures
Low M
high M
Chapter 5 - 14
MOLECULAR WEIGHT DISTRIBUTION
Fig. 5.4, Callister & Rethwisch 9e.
Chapter 5 - 18
Degree of Polymerization, DP
DP = average number of repeat units per chain
H H H H H H H H H H H H
H C C (C C ) C C C C C C C C H DP = 6
H H H H H H H H H H H H
secondary
bonding
Chapter 5 - 20
Polymers Molecular Shape
Molecular Shape (or Conformation) chain
bending and twisting are possible by rotation
of carbon atoms around their chain bonds
note: not necessary to break chain bonds
to alter molecular shape
Adapted from Fig.
5.5, Callister &
Rethwisch 9e.
Chapter 5 - 21
Chain End-to-End Distance, r
Chapter 5 - 22
Molecular Configurations for Polymers
Configurations to change must break bonds
Stereoisomerism
H H H H H R
C C C C or C C
H R
H R H H
A A
Stereoisomers are mirror
images cant superimpose C C
without breaking a bond E E
B D D B
mirror
plane
Chapter 5 - 23
Tacticity
Tacticity stereoregularity or spatial arrangement of R
units along chain
H H H H H H H H H H H R H H H R
C C C C C C C C C C C C C C C C
H R H R H R H R H R H H H R H H
Chapter 5 - 24
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
Chapter 5 - 25
cis/trans Isomerism
cis trans
cis-isoprene trans-isoprene
(natural rubber) (gutta percha)
H atom and CH3 group on H atom and CH3 group on
same side of chain opposite sides of chain
Chapter 5 - 26
VMSE: Stereo and Geometrical Isomers
A B
graft
Chapter 5 - 28
Polymer Crystals
Crystalline regions
thin platelets with chain folds at faces
Chain folded structure
10 nm
Chapter 5 - 29
Polymer Crystals (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
Fig. 14.11, Callister 6e. (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.)
Chapter 5 - 30
Polymer Single Crystals
Electron micrograph multilayered single crystals
(chain-folded layers) of polyethylene
Single crystals only for slow and carefully controlled
growth rates
1 m
Chapter 5 - 31
Semicrystalline Polymers
Some semicrystalline
polymers form
spherulite structures
Alternating chain-folded
crystallites and
amorphous regions
Spherulite structure for
relatively rapid growth
Spherulite rates
surface
Chapter 5 - 32
Photomicrograph Spherulites in
Polyethylene
Cross-polarized light used
-- a maltese cross appears in each spherulite
Core Problems:
Self-help Problems:
Chapter 5 - 34