Realistic polymer material
- Materials are in between Elastic solid and
Newtonian liquid called “viscoelastic”
- Some energy stored, some dissipated.
- Some time independent, some time dependent.
A typical viscoelastic effect is tackiness (with long strings)
which is not occuring with purely viscous liquid (example: water),
or purely elastic solid (example: stone)
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Viscoelastic Fluids
Viscoelastic behavior, illustrated by use of a dashpot and a spring
Polymers
Macromolecules are deformed and
at rest disentangled
Macromolecules are entangled low viscosity
and have spherical shapes
under shear
high viscosity
Physica Messtechnik Gmbh Vor dem lauch 6, 70567 Stuttgart, Germany Internet:[Link] .de
Newtonian and Non-Newtonian
Behavior of Fluids
1.000E5 Non-Newtonian 1.000E5
Newtonian Region Region
Independent of = f()
10000
Zero-shear viscosity (o)
1000
(Pa)
(Pa.s)
100.0
Shear thinning
Pseudo-plastic
10.00
10000 1.000
1.000E-5 1.000E-4 1.000E-3 0.01000 0.1000 1.000
shear rate (1/s)
Elastic Modulus vs. Temp.
4
brittle 3
E leathery
2
rubbery 1
viscous
Temp
Area 1: Viscous state:
Area 2: Rubbery state E = stress = F/A
= strain = dL/L
Area 3: Leathery state
Area 4: Glassy state E = elastic modulus
Linear and Non-Linear Stress-Strain
Behavior of Solids
1000 100.0
Linear Region Non-Linear Region
G is constant G = f()
100.0
osc. stress (Pa)
G
G' (Pa)
10.00
1.000 0.01000
0.010000 0.10000 1.0000 10.000 100.00 1000.0
% strain
Viscosity: Temperature dependence
10000
1000
viscosity (Pa.s)
100.0
10.00
20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0
temperature (Deg C)
Viscosity vs. Shear Rate
Result: Rheological material behaviour
Shear stress & viscosity as a function of the shear rate
• Newtonian
Ideal viscous (e.g.: oil, solvent)
• Shear thinning
(e.g.: typical food, cosmetics, coatings, polymers, …)
• Shear Thickening
Shear thickening (e.g.: PVC plastisol & paper coatings under high
shear cond.)
Newtonian and Non-Newtonian
Behavior of Fluids
1.000E5 Non-Newtonian 1.000E5
Newtonian Region Region
Independent of = f()
10000
1000
(Pa)
(Pa.s)
100.0
10.00
10000 1.000
1.000E-5 1.000E-4 1.000E-3 0.01000 0.1000 1.000
shear rate (1/s)
Idealized Flow Curve - Polymers
Power Law Region
First Newtonian Plateau
0 = Zero Shear
Viscosity
0 = K x MW3.4
Extend Range
log
with Time-
Temperature
Superposition (TTS)
Measure in Flow Mode on & Cox-Merz
AR1000/AR500
Extend Range Second Newtonian
with Oscillation Plateau
& Cox-Merz
Molecular Structure Compression Molding Extrusion Blow and Injection Molding
1.00E-5 1.00E-4 1.00E-3 0.0100 0.100 1.00 10.00 100.00 1000.00 1.00E4 1.00E5
shear rate (1/s)
Time-Dependent Viscoelastic Behavior:
Solid and Liquid Properties of "Silly Putty"
T is long [24 hours]
T ish o rt[< 1 s]
Deborah Number [De] = /
Some Types of Rheometers
• Typical Rheometer: • Capillary Rheometer:
Low shear rate/Oscillatory High shear rate
Rheology:Choosing Tests and Conditions
Geometries: Typical Rheometer
Max. 3°
Max. 3°
Delta < 1.2
Delta < 1.2
0.25mm < gap < 2mm
Ref.: Physica
Typical steady shear flow experiment
Polyethylene Rheology @ 150 C
1000000
HDPE
100000
LLDPE
viscosity (Pa.s)
10000
LDPE
1000
1.000E-4 1.00E-3 0.01000 0.1000 1.000 10.00
shear rate (1/s)
Idealized Full Flow Curve - Polymers
Power Law Region
First Newtonian Plateau
0 = Zero Shear
Viscosity
0 = K x MWc 3.4
Extend Range
log
with Time-
Temperature
Superposition (TTS)
Measure in Flow Mode on & Cox-Merz
AR1000/AR500
Extend Range Second Newtonian
with Oscillation Plateau
& Cox-Merz
Molecular Structure Compression Molding Extrusion Blow and Injection Molding
1.00E-5 1.00E-4 1.00E-3 0.0100 0.100 1.00 10.00 100.00 1000.00 1.00E4 1.00E5
shear rate (1/s)
At very high shear rate Melt fracture
Higher Shear Rate
Typical Oscillatory Data
PDMS
1.000E6 1.000E5 1.000E6
1.000E5 1.000E5
10000 10000
10000
1000 1000
G”
|n*| (Pa.s)
G' (Pa)
G'' (Pa)
100.0 100.0
10.00 G’ 10.00
1000
1.000 1.000
0.1000 0.1000
PDMS Extended frequency sweep-0001o, Frequency sweep step
0.01000 100.0 0.01000
1.000E-5 1.000E-4 1.000E-3 0.01000 0.1000 1.000 10.00 100.0
frequency (Hz)
4.2 Dynamic Temperature Ramp:
Material Response
Glassy Region
Transition
Region Rubbery Plateau
Region Terminal Region
log E' (G') and E" (G")
Storage Modulus (E' or G')
Loss Modulus (E" or G")
Temperature
