Thermal Transitions in Polymers

L3
Crystalline state
Under favorable conditions, some polymers cooled
from the melt can organize into regular crystalline
structures.

The basic units of crystalline polymer morphology are

crystalline lamellae
consisting of array of folded chains.

The solid state properties of Polymers 2

• For some polymers crystallized from the melt or
from concentrated solution,

• Crystallites can organize into larger spherical

structures called ‘SPHERULITES’

• Spherulites contains array of lamellar

ctystallites, oriented with the chain axis
perpendicular to the radial direction of the
spherulite.

The solid state properties of Polymers 3

Spherulite structure

The solid state properties of Polymers 4

 Polymer structure
• The polymer chain layout determines a lot of material properties:

• Amorphous:

• Crystalline:
Crystallinity in Polymers Adapted from Fig.
4.10, Callister &
• Polymers can be crystalline (i.e. Rethwisch 3e.
orderly arrangement)
• Ordered atomic arrangements
involving molecular chains

• Crystal structures in terms of unit cells

• Example shown
• polyethylene unit cell:
Orthorhombic

• However, given these are

large molecules as compared
to atoms/ions (i.e.
metals/ceramics) the crystal
structures/packing will be
much more complex
6
 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.

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.) 7
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
Structures of Polymers
• 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 )
s = overall density of the sample for which % is found

c = density of the crystalline part

a = density of the amorphous part

 Problem
The density and associated crystallinity of 2 polypropylene
materials are as follows”

Density(g/cc) Crystallinity(%)
0.904 62.8
0.895 54.4
(a) Compute density of the totally crystalline and totally
amorphous polypropylene
(b) Determine density of the polypropylene of 74.6% crystallinity
We are asked to compute the densities of totally crystalline and totally amorphous
polypropylene (ρc and ρa)
Let C=%crystallinity/100

In which ρs1= 0.904 g/cm3, ρs2= 0.895 g/cm3, C1= 0.628, and C2= 0.544. Solving the
above two equations for ρa and ρc leads to
(b) Now we are asked to determine the density of a specimen
having 74.6% crystallinity. Solving for ρs by using ρa and ρc which
were computed in part (a) yields
• Continued to next lecture