TE 570 Polymer Physics
Chapter 6. Mechanical and
Rheological Properties – Part B
Xiangwu Zhang
1
Outline
A Brief Review of Some Fundamentals
Mechanical Properties of Solid Polymers
Viscosity of Polymer Melts
Viscoelasticity of Polymers
Models of Viscoelastic Behavior
2
Several Interesting
Phenomena
Same viscosity Shear thinning
3
Several Interesting
Phenomena (cont’d)
Normal Stress Effect
4
Several Interesting
Phenomena (cont’d)
Secondary Flow
5
Several Interesting
Phenomena (cont’d)
Elastic Flow
6
http://www.aem.umn.edu/people/facult
y/joseph/particles/nano/nopart1.mpg 7
Several Interesting
Phenomena (cont’d)
8
Several Interesting
Phenomena (cont’d)
9
Several Interesting
Phenomena (cont’d)
Die swell
Will the polymer swell to the same extent?
10
Several Interesting
Phenomena (cont’d)
11
Viscosity of Polymer Melts
Deviation from Newtonian Flow
Effect of Molecular Weight
Several Important Polymer Processing
Methods
Melt Flow at High Strain Rates
Structure-Viscosity Relationships
Determination of Flow Curves
12
Viscosity of Polymer Melts
Mechanical properties Rheological properties
(deformation) (flow)
F
y
Shear stress: = f/A d
Shear strain: = /y Shear rate: dt
=G
elastic response viscous response
13
Deviation from Newtonian
Flow
A. Newtonian flow: water,
glycerol
B. Bingham flow: paint, pitch
C. Shear-thinning
(pseudoplastic) flow: most
polymer melts and solutions
D. Shear-thickening (dilatant)
flow: wet concrete, some
nanocomposites, polymers
that crystallize during flowing
14
Viscosity of Polymer Melts
Viscosity: The viscosity is a measure of the frictional forces
between the molecules in a liquid and depends upon factors
such as intermolecular forces and free volume
Shear-Thinning: In general, this type of behavior is due to
the chain “disentanglement” during shear
Shear-Thickening: Due to the formation of some
intermolecular forces
15
Apparent Viscosity
Theoretically, in a “shear-thinning” flow, there is
not a characteristic called “viscosity” (because
/
Shear stress
is not a constant )
By definition the apparent viscosity of polymer
is a function of shear stress or
melts and solutions
shear rate. a
Shear rate
General Expression
Newtonian flow: n = 1
Shear-thinning flow: n < 1 16
Zero Shear-Rate Viscosity
Zero shear-rate viscosity
Zero shear-rate viscosity is a characteristic parameter for describing
the behavior of polymers 17
Effect of Molecular Weight
1 .0
K LDPw
3 .4
K H DPw
DPw is a weight-average degree
of polymerization.
In some publications, DPw is the
weight average number of
carbon atoms in the main chain
18
Effect of Molecular Weight
(cont’d)
Log 0
Log DPw
19
Entanglement
K LDPw1.0
K H DPw3.4
20
Critical Molecular Weights and
DPc of Some Polymers (cont’d)
Mc DPc Mc DPc
Polyethylene 3500 250 Polyacrylonitrile 1300 50
Polypropylene 7000 330 Polybutadiene 6000 440
Polystyrene 35000 670 Polyisoprene 10000 590
Polyvinyl chloride 6200 200 Nylon-6 5000 310
Polymethyl Poly(ethylene
30000 600 6000 310
methacrylate terephthalate)
Polyvinyl acetate 25000 580 Polycarbonate 3000 140
What is the definition of DP in this table?
weight average number of carbon atoms in the main chain 21
Viscosity of Polymer Melts
3 .4
K H DPw
This would seem to make the (melt)
processing of high molecular weight
polymers an imposing if not
impossible task.
But, we are saved by two things: 1)
temperature effect, and 2) shear rate
effect. 22
Saver 1: Temperature Effect
There is an upper limit for increasing the processing temperature of
polymer melts, i.e., the degradation temperature
23
Saver 2: Shear-Thinning
24
Manufacturing methods
and typical shear rates
(1/s)
Compression moulding
Calendering
Extrusion
Injection moulding
25
Compression Molding
Squeeze molten
polymer between
hydraulic press
Shear rate: 1 to 10 s-1
26
Calendering
The material is passed through a series of heated rollers.
This process can produce rigid sheets, soft sheets, PVC
film, sponge sheets, artificial leather and others
Shear rate: 10 to 102 s-1
27
Extrusion
Control head pressure using screw angle and variable
die/shaft profile
Shear rate: 102 to 103 s-1
28
Injection Moulding
Control head pressure using screw angle and variable
die/shaft profile
Shear rate: 103 to 104 s-1
29
Other Processing Methods –
Film Blowing
Produce less oriented films than extrusion
30
Other Processing Methods –
Blow Moulding
Not to be confused with film blowing (which is
an extrusion-based process).
31
Manufacturing methods
and typical shear rates
(1/s)
Compression moulding 1 to 10
Calendering 10 to 10
Extrusion 102 to 10 3
njection moulding 103 to 10
32
Viscosity of Polymer Melts
Deviation from Newtonian Flow
Effect of Molecular Weight
Several Important Polymer Processing
Methods
Melt Flow at High Strain Rates
Structure-Viscosity Relationships
Determination of Flow Curves
33
Die Swell
It is governed by elastic
forces acting to deform the
polymer chains as they are
pushed into the die and as
they are sheared in the
narrow channel
Normal stress are developed
in the a direction
perpendicular to the flow
and deformation is ×
These stresses are relieved
recovered when the Dopolymer
not try to remember
exists the die, so the
these. The point here is the
extrudate swells die swell is complicated.
34
Effect of Temperature
35
Effect of Shear Rate
Impact on
polymer
processing?
36
Effect of Shear Stress
37
Melt Fracture
Shear rate, shear stress
There is a limit to the rate at which polymers can be extruded38
Viscosity of Polymer Melts
Deviation from Newtonian Flow
Effect of Molecular Weight
Several Important Polymer Processing
Methods
Melt Flow at High Strain Rates
Structure-Viscosity Relationships
Determination of Flow Curves
39
Effect of Chain Flexibility
Chains that are rigid and have large
intermolecular interaction
Nylon, polycarbonate, polyvinyl chloride, and polymethyl methacrylate
>
Polyethylene, polypropylene, polystyrene
40
Effect of Molecular Weight
.4
=3
.4
=3
pe
Slo
=1
pe
e
lop
Slo
1
p e=
o
Sl
Why is there no change here?
Shear rate ↑ more disentanglement lower slope
41
Effect of Molecular Weight
Distribution
At low shear rate, broader distribution more long chain higher
viscosity
At high shear rate, broader distribution more entanglements are being
disentangled lower viscosity
What it means is that viscosities of polymers with broader Mw distribution
are more sensitive since some entanglements come from very long
chains 42
Effect of Branching
In general, more (short)
branches longer
intermolecular distance,
weaker secondary bonding
forces lower viscosity
However, if the branches
are very long, more
entanglements higher
viscosity
43
Effect of Temperature
Arrhenius Equation:
This is true only at
E / RT
Ae T > Tg +100 oC
where ∆E: activation energy
A: structure constant
R: Boltzmann constant
Activation is defined as the energy that must be overcome
in order for a reaction (or process) to occur.
44
Effect of Temperature (cont’d)
1: PC (polycarbonate)
2: PE (polyethylene)
3: POM (polyoxymethylene)
4: PMMA (polymethyl
methacrylate)
5: cellulose acetate
6: nylon
Rigid polymer chains or stronger intermolecular force higher
activation energy more temperature sensitive
45
Impact on the processing?
Activation Energies of
Common Polymers
∆E, kJ/mol ∆E, kJ/mol
High-density
Polyisobutylene
polyethylene 2.51 50.2 – 67
(PIB)
(HDPE)
Low-density 46.1 – 71.2
Polyvinyl chloride
polyethylene (more branches, 94.6
(PVC)
(LDPE) higher ∆E)
Polyethylene
Polypropylene
41.9 terephthalate 58.6
(PP)
(PET)
Polystyrene (PS) 104.7
Rigid polymer chains or stronger intermolecular force higher
activation energy more temperature sensitive 46
Effect of Temperature - Our
Example
Will filler particles change the activation energy?
Sn-Pb (Tm = 183 -188 oC) + HDPE
In this particular case,
filler (solid or liquid)
does not change the
activity energy (i.e.,
the temperature
sensitivity of polymer
viscosity)
This is true only when
there is weak
interaction between the
filler and polymer 47
Effect of Shear Rate
1: polyether
2: polyethylene
3: polystyrene
4: cellulose acetate
5: polycarbonate
Flexible polymer chain easier to change chain
conformation easier to disentangle more shear
rate sensitive
48
Impact on the processing? Compare with temperature effect?
Effect of Shear Stress
1: polyoxymethylene
2: polycarbonate
3: polyethylene
4: polymethyl methacrylate
5: cellulose acetate
6: nylon
Similar to shear rate
49
In Processing
In order to reduce the viscosity
For flexible chains, increase the shear rate
For rigid chains or chains with strong
intermolecular force, increase the temperature
50
Effect of Pressure
In extrusion, injection, etc., high pressure is
applied
LDPE
This is important in
polymer processing
1
51
Viscosity of Polymer Melts
Deviation from Newtonian Flow
Effect of Molecular Weight
Several Important Polymer Processing
Methods
Melt Flow at High Strain Rates
Structure-Viscosity Relationships
Determination of Flow Curves √
52
Falling-Ball Rheometer
Ball
ρs
Heating Element
Sample
ρl
K: instrument constant
t: time for dropping the ball
from a to b
Can only be used to study viscosity at low shear rates
Can be used to measure the zero shear-rate viscosity 53
Capillary Rheometer
54
Capillary Rheometer (cont’d)
How do we get this?
Rp p 4Q
wall wall ( apparent ) 3
2L 2L
R
R
L is length of capillary Q volumetric throughput
R radius of capillary
p pressure change
R 2 P 2RL
P R
2L 55
Capillary Rheometer (cont’d)
Before plotting shear viscosity versus shear
rate, you need
Apply Weissenberg-Rabinowitsch correction for no
parabolic velocity profile – calculate “correct”
shear rate at the wall √
Correct the stress measurements for entrance and
exit effects (Bagley Correction)
Look for slip effects (Mooney Plot); correct data
56
Capillary Rheometer – My
Example
Sn-Pb + polystyrene at 195oC
57
Melt Indexer
Melt index refers to the grams of polymer extruded in 10
min. Dimensions of die, temperature and pressure must
be specified. ASTM D1238 is for polyethylene.
58
Rotational Rheometer
Ф
Rotational
rheometers can be
used in the steady
state or in a dynamic Ф
mode (we will
discuss this later)
59
Rheological Methods
Shear Rate, s-1 Viscosity, Pa.s
Falling-Ball
<<10-2 10-3 - 103
Rheometer
Capillary
100 - 106 10-1 - 107
Rheometer
Parallel Plates: 103 - 108
Rotational
10-3 - 102 Cone and Plate: 102 - 1011
Rheometer
Concentric cylinder: 10-1 - 1011
Melt Indexer 100 - 102 103 - 104
60
Rheological Instrumentation
61
One Example
Rheometrics Scientific, - ARES - Advanced Rheometric
Expansion System
62
A Brief Review of Some Fundamentals
Mechanical Properties of Solid Polymers
Viscosity of Polymer Melts
Viscoelasticity of Polymers
Models of Viscoelastic Behavior
63
