Chapter 4:

Polymer Structures (고분자 구조)

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 4 - 1
 What is a Polymer?

Poly mer
many repeat unit

repeat repeat repeat

unit unit unit
H H H H H 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 C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3
Polyethylene (PE) Poly(vinyl chloride) (PVC) Polypropylene (PP)
Adapted from Fig. 4.2, Callister & Rethwisch 5e.

Chapter 4 - 2
 Ancient Polymers
• Originally natural polymers were used
– Wood – Rubber
– Cotton – Wool
– Leather – Silk

• Oldest known uses

– Rubber balls used by Incas
– Use of pitch (a natural polymer)
to seal boat seams

Chapter 4 - 3
 Polymer Composition
Most polymers are hydrocarbons
– i.e., made up of H and C
• Saturated hydrocarbons (포화 탄화수소)
– Each carbon singly bonded to four other atoms
– Example:
• Ethane, C2H6
H H
H
C C

H H
H

Chapter 4 - 4
Chapter 4 - 5
 Unsaturated Hydrocarbons
(불포화 탄화수소)
• Double & triple bonds somewhat unstable –
can form new bonds
– Double bond (이중결합) found in ethylene or
ethene - C2H4
H H
C C
H H

– Triple bond (삼중결합) found in acetylene or

ethyne - C2H2
H C C H
Chapter 4 - 6
 Isomerism (이성질)
• Isomerism (이성질)
– 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 4 - 7
 Polymerization (중합) and
Polymer Chemistry
• Free radical polymerization (자유 라디컬 중합)
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(개시제): example - benzoyl peroxide

H H H
C O O C 2 C O =2R
H H H

Chapter 4 - 8
 Chemistry and Structure of
Polyethylene
Adapted from Fig.
4.1, Callister &
Rethwisch 5e.

Note: polyethylene is a long-chain hydrocarbon

- paraffin wax for candles is short polyethylene

Chapter 4 - 9
Bulk or Commodity Polymers

Chapter 4 - 10
Bulk or Commodity Polymers (cont)

Chapter 4 - 11
Bulk or Commodity Polymers (cont)

Chapter 4 - 12
VMSE: Polymer Repeat Unit Structures

Manipulate and rotate polymer structures in 3-dimensions

Chapter 4 - 13
 MOLECULAR WEIGHT (분자량)
• Molecular weight (분자량), M: Mass of a mole of chains.

Low M

high M

Not all chains in a polymer are of the same length

— i.e., there is a distribution of molecular weights

Chapter 4 - 14
 MOLECULAR WEIGHT DISTRIBUTION
Adapted from Fig. 4.4, Callister & Rethwisch 5e.

total wt of polymer
Mn =
total # of molecules

M n = Sx i M i
M w = Sw i M i

Mi = mean (middle) molecular weight of size range i

xi = number fraction of chains in size range i
wi = weight fraction of chains in size range i
Chapter 4 - 15
 Molecular Weight Calculation
Example: average mass of a class
Student Weight
mass (lb) Average weight of the students in
1 104 This class?
2 116
3 140 a) Based on the number fraction of
4 143 students in each mass range?
5 180
6 182 b) Based on the weight fraction of
7 191
students in each mass range?
8 220
9 225
10 380
Chapter 4 - 16
 Molecular Weight Calculation (cont.)
Solution: The first step is to sort the students into weight ranges.
Using 40 lb ranges gives the following table:

weight number of mean Calculateweight

number the number and weight
fraction of students in each weight
range students weight fraction fraction
range as follows:
Ni Wi xi w NiWi
Ni i
xi = wi =
å0.117 å NiWi
mass (lb) mass (lb)
Ni
81-120 2 110 0.2
121-160 2 142 0.2 0.150
161-200 3 184 For example:
0.3 0.294for the 81-120 lb range
201-240 2 223 0.2 0.2372
241-280 0 - =
0 x81-1200.000 = 0.2
10
281-320 0 - 0 0.000
2 x 110
81-120 = = 0.117
321-360 0 - 0 w 0.000
361-400 1 380 0.1 0.202 1881

total SNi SNiWi total

number 10 1881 weight Chapter 4 - 17
 Molecular Weight Calculation (cont.)
weight mean number weight
range weight fraction fraction
Wi xi wi
mass (lb) mass (lb)
81-120 110 0.2 0.117
121-160 142 0.2 0.150
161-200 184 0.3 0.294
201-240 223 0.2 0.237
241-280 - 0 0.000
281-320 - 0 0.000
321-360 - 0 0.000
361-400 380 0.1 0.202
Mn = å xi Mi = (0.2 x 110 + 0.2 x 142 + 0.3 x 184 + 0.2 x 223 + 0.1 x 380) = 188 lb
Mw = å wi Mi = (0.117 x 110 + 0.150 x 142 + 0.294 x 184
+ 0.237 x 223 + 0.202 x 380) = 218 lb
Mw = å wi Mi = 218 lb
Chapter 4 - 18
 Degree of Polymerization(중합도),
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

Chain fraction mol. wt of repeat unit i

Chapter 4 - 19
Molecular Structures for Polymers

secondary
bonding

Linear Branched Cross-Linked Network

Adapted from Fig. 4.7, Callister & Rethwisch 5e.

Chapter 4 - 20
 Polymers – Molecular Shape
Molecular Shape (or Conformation(입체형태))
– 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.
4.5, Callister &
Rethwisch 5e.

Chapter 4 - 21
Chain End-to-End Distance, r

Adapted from Fig.

4.6, Callister &
Rethwisch 5e.

Chapter 4 - 22
 Molecular Configurations for Polymers
Configurations (배위) – to change must break bonds
• Stereoisomerism (입체이성질체)

H H H H H R
C C C C or C C
H R
H R H H

A A
Stereoisomers(입체이성질체) are mirror images
=> can’t superimpose without breaking a bond C C
E E
B D D B
mirror
plane

Chapter 4 - 23
 Tacticity (입체 규칙도)
Tacticity (입체규칙도) – stereoregularity(입체규칙성) 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 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 4 - 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 4 - 25
 cis/trans Isomerism

CH3 H CH3 CH2

C C C C
CH2 CH2 CH2 H

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 4 - 26
 Copolymers (공중합체) Adapted from Fig.
4.9, Callister &
Rethwisch 5e.

Two or more monomers random

polymerized together

• random – A and B randomly

positioned along chain
alternating
• alternating – A and B alternate in
polymer chain
block
• block – large blocks of A units
alternate with large blocks of B
units

• graft – chains of B units grafted

onto A backbone
graft

A– B– Chapter 4 - 27
 Crystallinity (결정성) in Polymers
Adapted from Fig.
4.10, Callister &
Rethwisch 5e.

• Ordered atomic
arrangements involving
molecular chains

• Crystal structures in terms

of unit cells

• Example shown
– polyethylene unit cell

Chapter 4 - 28
 Polymer Crystallinity (결정성)
• Crystalline regions
– thin platelets with chain folds at faces
– Chain folded structure

Adapted from Fig.

4.12, Callister &
Rethwisch 5e.

≈ 10 nm

Chapter 4 - 29
 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 amorphous
region
increase.
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 4 - 30
 Polymer Single Crystals
• Electron micrograph – multilayered single crystals
(chain-folded layers) of polyethylene
• Single crystals – only for slow and carefully controlled
growth rates

Fig. 4.11, Callister &

Rethwisch 5e.
[From A. Keller, R. H. Doremus, B.
W. Roberts, and D. Turnbull (Eds.),
Growth and Perfection of Crystals.
General Electric Company and
John Wiley & Sons, Inc., 1958, p.
498. Reprinted with permission of
John Wiley & Sons, Inc.]

1 μm
Chapter 4 - 31
Semicrystalline (반결정질) Polymers
• Some semicrystalline
polymers form spherulite
structures

• Alternating chain-folded
crystallites and amorphous
regions

• Spherulite structure for

relatively rapid growth rates
Spherulite
surface

Adapted from Fig. 4.13, Callister & Rethwisch 5e.

Chapter 4 - 32
 Photomicrograph –
Spherulites in Polyethylene
Cross-polarized light used
→ a maltese cross (몰타 십자) appears in each spherulite

Courtesy F. P. Price, General Electric Company

100 μm

Fig. 4.14, Callister & Rethwisch 5e.

Chapter 4 - 33
 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 4 - 34