Crystallinity

Amorphous vs. crystalline

Amorphous - Random orientation of chains
- Above Tg: flexible, ductile and soft.
Crystalline - Repeatable 3D structure of polymer units
- Higher tensile (and shear) moduli and strengths
- Possibly more brittle.
- Because polymer chains are long, when Xtzn occurs
any polymer chain may be in more than one
crystallite.
- This inhibits mobility and segments in between
cannot enter crystal structure.
- Polymers are thus semi-crystalline (20-80%).
- These amorphous regions make these polymers tough
rather than brittle.
 Crystallization
3-D structure is regular close-packed crystal lattice

Require
• stereoregularity (i.e. high isotacticity, syndiotacticity, cis or trans
• smaller side groups. Bulky groups impede mobility leading to
lower crystallinity .
• lower branching.
• possible internal stabilization - hydrogen bonding.
• orientation by stress – tensile, drawing, dies, etc.
 H-bonding in nylons
O

O H N

O H N

H N

N H

N H O

N H O

O H N

O H N

H N
PE Crystallization
Lamellae

Folded re-entry model

 Spherulites

Bending of lamellae. Include amorphous material.

PP crystallization

Maltese cross forms under

polarization
Single crystals

PE crystal grown from

solution
 Shish-kebab
of is dit net ‘n sosatie?

Shearing during crystallization

 Fringed micelles

Controversial. Possible under stress-crystallization

Maybe at low crystallinity. Stabilized by VDW forces.
 Control of crystallization
• Choice of polymer grade.
• Cooling conditions (temperature or rate).
• Crash cooling leads to amorphous lock-in.
• Additives to promote or suppress.
• Plasticizers can suppress crystallization (impurities).
• Filler surfaces may promote crystallization.
• Nucleating agents may promote nucleation rather than
crystal growth. Control of transparency.
 Crystallization and properties
10000
Dynamic shear modulus, G' (/ MPa)

1000

100

10

1
-160 -120 -80 -40 0 40 80 120 160
Temperature (/ oC)

HDPE
Crystallization and properties
 Rate of crystallization

Tg Tm Maximum below Tm
Rate of Eight-ninths rule
crystallization

Driving force (G) increases

as T drops

But simultaneously chain

Temperature mobility drops.

External surfaces cool faster and may consequently have lower

degrees of crystallinity.
 Avrami equation
1

0.9

0.8

0.7

0.6

X(t )  X  1  e Zt n

n= 1
X(t)

0.5
n= 2
n= 3
0.4

0.3

0.2

0.1

0
Time

n = 4 for spherulites, n = 3 for discs, n = 2 for rods

Reduce by 1 for instantaneous nucleation
 Crystallization and polymer type

Polymer Growth Maximum

rate (/ min-1) crystallinity

Polyethylene(PE) > 1000 80

Nylon 6,6’ 1000 70
Nylon 6 200 35
isotactic polypropylene (i-PP) 20 63
poly(ethylene terephthalate) (PET) 7 50
isotactic polystyrene (i-PS) 0.30 32
polycarbonate (PC) 0.01 25
 Crystallinity determination

Density measurements

c  sample   am
Mass based 100
 sample  c   am

Volume based
 sample   am
100
 c   am
 Density and volume based methods

Dilatometry – volume changes with temperature

Density gradient column – 2 miscible solutions straddling density
range. Use standards.
Floatation – titration of miscible liquids
Density bottle

M liquid   M t  M b  Ms 
VS 
 liquid
 Differential scanning calorimetry (DSC)

Measure heat flow as a function of temperature

Cold crystallization Curing, oxidation, crosslinking

exo

Degradation
Tg
Melt, Tm
 Differential scanning calorimetry (DSC)

Measure heat flow as a function of temperature.

Quantify enthalpy of melting.
Measure relative to pure crystalline polymer.
Latter determined by extrapolation on standards.

H f ,s
Wc  100
H f ,c
 FTIR

Measure absorbance of crystalline and amorphous bands.

Ac
Am
Wc  100
Ac
K
Am
K is polymer specific. Depends on relative extinction coefficients
of crystalline and amorphous bands.
 XRD

 I c (s).ds
2
s
Wc  o


 I(s).ds
2
s
o

2 sin 
s
