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Polymer Crystallinity

There are three main physical states that polymers can take: amorphous, crystalline, and liquid. As temperature increases, polymers transition from crystalline to liquid through an amorphous or "gum" phase. Various techniques can be used to characterize and quantify polymer crystallinity, including differential scanning calorimetry (DSC), dilatometry, and wide-angle X-ray scattering/diffraction. DSC is a common method that relates heat of fusion measurements to literature values for 100% crystalline polymers. Crystallinity estimates from different techniques can be combined for the most accurate assessment. Understanding polymer crystallinity is important because it contributes significantly to material strength in many polymers.

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Kaushal Singh
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56 views21 pages

Polymer Crystallinity

There are three main physical states that polymers can take: amorphous, crystalline, and liquid. As temperature increases, polymers transition from crystalline to liquid through an amorphous or "gum" phase. Various techniques can be used to characterize and quantify polymer crystallinity, including differential scanning calorimetry (DSC), dilatometry, and wide-angle X-ray scattering/diffraction. DSC is a common method that relates heat of fusion measurements to literature values for 100% crystalline polymers. Crystallinity estimates from different techniques can be combined for the most accurate assessment. Understanding polymer crystallinity is important because it contributes significantly to material strength in many polymers.

Uploaded by

Kaushal Singh
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Physical State Transitions

Amorphous Polymer Crystalline Polymer


Increasing Temperature  Liquid Liquid
Tm

Gum Flexible
Thermoplastic

Rubber
Tg
Tg
Glass
Crystalline Structures
Spherulite Morphology “Re-entry”
Folding and “Re-entry”

Youyong Li and William A. Goddard III


Macromolecules 2002 35 (22), 8440-8455
(from Odian)
Crystallinity by DSC
 Experiment Setup
Crystallinity by DSC
 Example: ∆H obs
%Crystallinity = ×100%
f
Crystallinity of ∆H °
f

Polyethylene Table: Heats of fusion of 100%


crystalline polymers

Q: “Where is my polymer in
this table?”
Dilatometry
Dilation or change in
specific volume Computing crystallinity

∆V

Liquid of
known density
and thermal
expansion
coefficient

vamorphous − v partially crystalline


Polymer %C =
vamorphous − vtotally crystalline
Dilatometry

 Example: Nylon
 How would you find
the density (i.e.
specific volume) of
this crystal given the
size and shape?

vamorphous − v partially crystalline


%C =
vamorphous − vtotally crystalline
Youyong Li and, William A. Goddard III
Macromolecules 2002 35 (22), 8440-8455
Wide angle x-ray
scattering/diffraction
 X-rays: light with
X-rays:
~0.1-
wavelength ~0.1-
10Å – the same
10Å
length scale as
interatomic
distances
 Diffraction occurs
nλ = 2d sin θ
only at specific
angles, given by the
Bragg eqn.
X-ray Scattering Crystal Planes

nλ = 2d sin θ
Wide angle x-ray
scattering/diffraction

θ?
Why 2θ
What if it’s not a single crystal?

 Polycrystalline
samples look
different.
 Example: Highly
crystalline polymer
with (mostly)
oriented crystallites.
 Diffraction spots are
blurred into lines.
What if it’s not a single crystal?

 Polycrystalline
samples look
different.
 Example: Highly
crystalline polymer
with no orientation
of crystallites.
 Diffraction spots are
blurred into full
circles.
What if it’s not crystalline?

 Diffraction circles
become much less
defined and blurred.
 Sharpness of circles
gives a clue to
crystallinity.
An estimate of crystallinity

 The crystallinity can be
estimated by comparing
the areas of the peaks
due to the amorphous
polymer with those of
the crystalline phase:

%C=A cr / (A cr + A am)

K.A. Moly et al. / European Polymer Journal 41


(2005) 1410–1419;
Example: Strain-induced
Crystallization

S. Toki et al. / Polymer 41 (2000) 5423–


5429
Other methods: IR & NMR

Ying Zheng,, Merlin L. Bruening, and,


Gregory L. Baker
Macromolecules 2007 40 (23), 8212-
8219
Conclusion: A comparison
Method of Advantages Disadvantages
Analysis
Differential Fast, easy; You’re probably Need literature values of
Scanning going to use DSC anyway for Tg, heat of fusion for 100%
Calorimetry etc. crystalline polymer for
comparison; thermal
history an issue.

Dilatometry A simple way to measure Pure crystalline specific


polymer crystallinity based on volume must be known.
changes in volume.
X-ray scattering Can determine precise crystal Difficult to analyze data,
structure. determine structure.

Polarized Optical A quick way to see if a polymer Other factors (like strain
Microscopy is crystalline. in the polymer) can
cause birefringence;
difficult to quantify.
Conclusion

 Offshoot: A combination of methods


x-ray
may be the best solution (e.g. x-ray
scattering, DSC)
 Polymer crystallinity contributes to the
strength of many polymeric materials.
 Questions?
The Crystalline
Melting Temperature

Semi-crystalline
Solid

Heat

Melt
Characteristics: Melting
Temperatures
Temperature (0 C) 40

20

Melting is Complete
0

Melting Starts
-20 Crystallization

-40
-50 -40 -30 -20 -10 0 10

Temperature of Crystallization
Thermodynamic Considerations
Excess Free energy of
surface per unit area = σe

x
Excess Free energy of
crystal edge per unit area = σ
∆ Gcryst = (4xl)σ + 2
σ
(2x ) e (x l)∆ g
- 2
Extended Chain Crystals

∆ cryst =
G (4xl)σ + (2x
2
)σ e -
(x
2
l)∆ g

∆ Gcryst = 2x 2 [(2l/x )σ + σ e] - (x 2 l)∆ g

For x > > l;

∆ Gcryst = 2x 2 σ e - (x 2 l)∆ g

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