02 Polymers

Polymers 2
4.11 Polymer structure

• The polymer chain layout determines a lot of material
properties:
• Amorphous:
• Crystalline:
Crystallinity in Polymers Adapted from Fig.
4.10, Callister &
Rethwisch 3e.
• Ordered atomic
arrangements involving
molecular chains
• Crystal structures in terms
of unit cells
• Example shown
– polyethylene unit cell
– Polymers can be crystalline (i.e.
have long range order)
– However, given these are large
molecules as compared to
atoms/ions (i.e. metals/ceramics)
the crystal structures/packing
will be much more complex
Chapter 4 - 3
Structures of Polymers
• Polymer crystallinity
– (One of the) differences between small molecules and
polymers
– Small molecules can either totally crystallize or
become an amorphous solid
– Polymers often are only partially crystalline
• Why? Molecules are very large
• Have crystalline regions dispersed within the remaining
amorphous materials
• Polymers are often referred to as semicrystalline
• Polymer crystallinity
– Another way to think about it is that these are two
phase materials (crystalline, amorphous)
– Need to estimate degree of crystallinity – many ways
• One is from the density
 c ( s −  a )
%crystallinity = 100
 s ( c −  a )
4.11 Polymer crystallinity

– What influences the degree of crystallinity
• Rate of cooling during solidification
• Molecular chemistry – structure matters
– Polyisoprene – hard to crystallize
– Polyethylene – hard not to crystallize
• Linear polymers are easier to crystallize
• Side chains interfere with crystallization
• Stereoisomers – atactic hard to crystallize (why?); isotactic,
syndiotactic – easier to crystallize
• Copolymers – more random; harder to crystallize
4.11 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.) Chapter 4 - 7
4.11 MOLECULAR WEIGHT & CRYSTALLINITY
• Molecular weight, Mw: Mass of a mole of chains.
• Tensile strength (TS):

--often increases with Mw.
--Why? Longer chains are entangled (anchored) better.
• % Crystallinity: % of material that is crystalline.
--TS and E often increase
with % crystallinity. crystalline
--Annealing causes region
crystalline regions
to grow. % crystallinity amorphous
region
increases. 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.) 4Chapter 4 -
4.12 Polymer Crystallinity
4.12 Polymer crystals
– Chain folded-model
• Many polymers crystallize as very thin platelets (or
lamellae)
• Idea – the chain folds back and forth within an individual
plate (chain folded model)
• Crystalline regions
– thin platelets with chain folds at faces
– Chain folded structure Chapter 4 -
4.12 Single Crystals
• Electron micrograph – multilayered single crystals
(chain-folded layers) of polyethylene
• Single crystals – only for slow and carefully controlled
growth rates
Adapted from Fig. 4.11, Callister & Rethwisch 3e.

Chapter 4 - 10
4.12 Semicrystalline Polymers
• Some semicrystalline
polymers form
spherulite structures
• Alternating chain-folder
crystallites and
amorphous regions
• Spherulite structure for
relatively rapid growth
Spherulite rates
surface
Adapted from Fig. 4.13, Callister & Rethwisch 3e.
Chapter 4 - 11
• Polymer crystals
– More commonly, many polymers that crystallize from a melt form
spherulites
• One way to think of these – the chain folded lamellae have
amorphous “tie domains” between them
• These plates pack into a spherical shape
• Polymer analogues of grains in polycrystalline
metals/ceramics
Photomicrograph – Spherulites in Polyethylene
Cross-polarized light used
-- a maltese cross appears in each spherulite
Adapted from Fig. 4.14, Callister & Rethwisch 3e. Chapter 4 - 13

stress–strain behavior
for brittle (curve A),
plastic
(curve B), and highly
elastic (elastomeric)
(curve C) polymers.
Chapter 4 - 14
Stages in the elastic deformation of a semicrystalline polymer. (a) Two adjacent chain-folded lamellae and
interlamellar amorphous material before deformation. (b) Elongation of amorphous tie chains during the first
stage of deformation. (c) Increase in lamellar crystallite thickness (which is reversible) due to bending and
stretching of chains in crystallite regions. (From Schultz, Jerold M., Polymer Materials Science, 1st edition, ©
1974, pp. 500, 501.Adapted by permission of Pearson Education, Inc., Upper Saddle River, NJ.
Chapter 4 - 15
Stages in the plastic deformation of a semicrystalline polymer. (a) Two adjacent chain-folded lamellae and
interlamellar amorphous material after elastic deformation (also shown as Figure 15.12c). (b) Tilting of lamellar chain
folds. (c) Separation of crystalline block segments. (d) Orientation of block segments and tie chains with the tensile
axis in the final plastic deformation stage. (From Schultz, Jerold M., Polymer Materials Science, 1st edition, 1974, pp.
500, 501. Adapted by permission of Pearson Education, Inc., Upper Saddle River, NJ.)
Chapter 4 - 16
Specific volume versus
temperature, upon cooling from the
liquid melt, for totally amorphous
(curve A), semicrystalline (curve B),
and crystalline (curve C) polymers
Chapter 4 - 17
Schematic diagram of a
compression molding apparatus.
(From F.W. Billmeyer, Jr.,
Textbook
of Polymer Science, 3rd
edition. Copyright 1984 by John
Wiley & Sons, New York.
Reprinted by permission
of John Wiley & Sons,
Inc.)
Chapter 4 - 18
Schematic diagram of an
injection molding apparatus.
(Adapted from
F.W. Billmeyer, Jr., Textbook
of Polymer Science, 2nd
edition. Copyright 1971 by
John Wiley & Sons, New
York.
Chapter 4 - 19
Schematic diagram of an extruder. (Reprinted with permission from
Encyclopædia Britannica, © 1997 by Encyclopædia Britannica, Inc.)
Chapter 4 - 20
Blow molding process
Chapter 4 - 21
Chapter 4 - 22

02 Polymers

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Polymers 2

4.11 Polymer structure

4.11 Polymer crystallinity

• Tensile strength (TS):

Adapted from Fig. 4.11, Callister & Rethwisch 3e.

Adapted from Fig. 4.13, Callister & Rethwisch 3e.

Adapted from Fig. 4.14, Callister & Rethwisch 3e. Chapter 4 - 13

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