1. Introduction to Viscoelasticity
All viscous liquids deform continuously under the influence of an applied stress – They exhibit viscous behavior.
Solids deform under an applied stress, but soon reach a position of equilibrium, in which further deformation ceases. If the stress is removed they recover their original shape – They exhibit elastic behavior.
Viscoelastic fluids can exhibit both viscosity and elasticity, depending on the conditions.
Viscous fluid
Viscoelastic fluid
Elastic solid
Polymers display VISCOELASTIC properties

2. A Demonstration of Polymer Viscoelasticity
Poly(ethylene oxide) in water

3. “Memory” of Previous State
Poly(styrene)
Tg ~ 100 °C

4. Chapter 5. Viscoelasticity
Is “silly putty” a solid or a liquid?
Why do some injection molded parts warp?
What is the source of the die swell phenomena that is often observed in extrusion processing?
Expansion of a jet
of an 8 wt% solution of
polyisobutylene in decalin
Polymers have both Viscous (liquid) and elastic (solid) characteristics

5. Measurements of Shear Viscosity
Melt Flow Index
Capillary Rheometer
Coaxial Cylinder Viscometer (Couette)
Cone and Plate Viscometer (Weissenberg rheogoniometer)
Disk-Plate (or parallel plate) viscometer

6. Weissenberg Effect

7. Dough Climbing: Weissenberg Effect
Other effects:
Barus
Kaye

8. Rheology is the science of flow and deformation of matter
What is Rheology?
Rheology is the science of flow and deformation of matter
Rheology Concepts, Methods, & Applications, A.Y. Malkin and A.I. Isayev; ChemTec Publishing, 2006

11. Time dependent processes: Viscoelasticity
The response of polymeric liquids, such as melts and solutions, to an imposed stress may resemble the behavior of a solid or a liquid, depending on the situation.
•Liquid favored by longer time scales & higher temperatures
• Solid favored by short time and lower temperature
De is large, solid behavior, small-liquid behavior.

13. increasing loading rate
Stress
Strain
increasing loading rate

14. Time and temperature

15. Network of Entanglements
There is a direct analogy between chemical crosslinks in rubbers and “physical” crosslinks that are created by the entanglements.
The physical entanglements can support stress (for short periods up to a time tT), creating a “transient” network.

16. Entanglement Molecular Weights, Me, for Various Polymers
Me (g/mole)
Poly(ethylene) 1,250
Poly(butadiene) 1,700
Poly(vinyl acetate) 6,900
Poly(dimethyl siloxane) 8,100
Poly(styrene) 19,000

17. Pitch drop experiment
Started in 1927 by University of Queensland Professor Thomas Parnell.
A drop of pitch falls every 9 years
Pitch drop experiment apparatus
Pitch can be shattered by a hammer

18. Viscoelasticity and Stress Relaxation
Whereas steady-shear measurements probe material responses under a steady-state condition, creep and stress relaxation monitor material responses as a function of time.
Stress relaxation studies the effect of a step-change in strain on stress. ?

19. Physical Meaning of the Relaxation Time
Constant strain applied
time s
Stress relaxes over time as molecules re-arrange
time
Stress relaxation:

20. Static Testing of Rubber Vulcanizates
Static tensile tests measure retractive stress at a constant elongation (strain) rate.
Both strain rate and temperature influence the result
Note that at common static test conditions, vulcanized elastomers store energy efficiently, with little loss of inputted energy.

21. Dynamic Testing of Rubber Vulcanizates: Resilience
Resilience tests reflect the ability of an elastomeric compound to store and return energy at a given frequency and temperature.
Change of rebound
resilience (h/ho) with
temperature T for:
1. cis-poly(isoprene);
2. poly(isobutylene);
3. poly(chloroprene);
4. poly(methyl methacrylate).

22. Mathematical models: Hooke and Newton
It is difficult to predict the creep and stress relaxation for polymeric materials.
It is easier to predict the behaviour of polymeric materials with the assumption  it behaves as linear viscoelastic behaviour.
Deformation of polymeric materials can be divided to two components:
Elastic component – Hooke’s law
Viscous component – Newton’s law
Deformation of polymeric materials  combination of Hooke’s law and Newton’s law.

23. Hooke’s law & Newton’s Law
The behaviour of linear elastic were given by Hooke’s law: or
The behaviour of linear viscous were given by Newton’s Law:
E= Elastic modulus
s = Stress
e = strain
de/dt = strain rate
ds/dt = stress rate
= viscosity
** This equation only applicable at low strain

24. Viscoelasticity and Stress Relaxation
Stress relaxation can be measured by shearing the polymer melt in a viscometer (for example cone-and-plate or parallel plate). If the rotation is suddenly stopped, ie. g=0, the measured stress will not fall to zero instantaneously, but will decay in an exponential manner. .
Relaxation is slower for Polymer B than for Polymer A, as a result of greater elasticity.
These differences may arise from polymer microstructure (molecular weight, branching).

25. STRESS RELAXATION
CREEP
Constant strain is applied  the stress relaxes as function of time
Constant stress is applied  the strain relaxes as function of time

26. Time-dependent behavior of Polymers
The response of polymeric liquids, such as melts and solutions, to an imposed stress may under certain conditions resemble the behavior of a solid or a liquid, depending on the situation.
Reiner used the biblical expression that “mountains flowed in front of God” to define the DEBORAH number

27. metal
elastomer
Viscous liquid

28. Static Modulus of Amorphous PS
Glassy
Leathery
Rubbery
Viscous
Polystyrene
Stress applied at x
and removed at y

29. Stress Relaxation Test
Strain
Elastic
Stress
Stress
Viscoelastic
Stress
Viscous fluid
Viscous fluid
Viscous fluid
Time, t

30. Stress relaxation Go (or GNo) is the “plateau modulus”:
Stress relaxation after a step strain go is the fundamental way in which we define the relaxation modulus:
Go (or GNo) is the “plateau modulus”:
where Me is the average mol. weight between entanglements
G(t) is defined for shear flow. We can also define a relaxation modulus for extension:
stress
strain
viscosity
Gmodulus

31. Stress relaxation of an uncrosslinked melt
perse
Glassy behavior
Transition Zone
Terminal Zone
(flow region)
slope = -1
Plateau Zone
Mc: critical molecular weight above which entanglements exist
3.24

33. Mechanical Model
Methods that used to predict the behaviour of visco-elasticity.
They consist of a combination of between elastic behaviour and viscous behaviour.
Two basic elements that been used in this model:
Elastic spring with modulus which follows Hooke’s law
Viscous dashpots with viscosity h which follows Newton’s law.
The models are used to explain the phenomena creep and stress relaxation of polymers involved with different combination of this two basic elements.

34. Dynamic Viscosity (dashpot)
Shear stress
Lack of slipperiness
Resistance to flow
Interlayer friction
SI Unit: Pascal-second
Shear rate
1 centi-Poise = milli Pascal-second
stress
strain
viscosity
Gmodulus

35. Ideal Liquid h= viscosity de/dt = strain rate
The viscous response is generally time- and rate-dependent.

36. Ideal Liquid

37. Ideal (elastic) Solid Hooks Law
response is independent of time and the deformation is dependent on the spring constant.

38. Ideal Solid

39. Polymer is called visco- elastic because:
Showing both behaviour elastic & viscous behaviour
Instantaneously elastic strain followed by viscous time dependent strain
Load released
elastic
Load added
viscous
viscous
elastic

40. stress
strain
viscosity
Gmodulus

41. Maxwell Model

42. Kelvin Voigt Model

43. Burger Model

44. Static Modulus of Amorphous PS
Glassy
Leathery
Rubbery
Viscous
Polystyrene
Stress applied at x
and removed at y

45. Dynamic Mechanical Analysis

46. Spring Model g = g0⋅sin (ω⋅t) g0 = maximum strain w = angular velocity
Since stress, t, is
t = Gg
t = Gg0sin(wt)
And t and g are in phase

47. Whenever the strain in a dashpot is at its maximum, the rate of change of the strain is zero ( g = 0).
Whenever the strain changes from positive values to negative ones and then passes through zero, the rate of strain change is highest and this leads to the maximum resulting stress.
Dashpot Model

48. Kelvin-Voigt Model

49. Courtesy: Dr. Osvaldo Campanella

50. Dynamic Mechanical Testing Response for Classical Extremes
Purely Viscous Response
(Newtonian Liquid)
Purely Elastic Response
(Hookean Solid)
 = 90°
 = 0°
Stress
Stress
Strain
Strain
Courtesy: TA Instruments

51. Dynamic Mechanical Testing Viscoelastic Material Response
Phase angle 0° < d < 90°
Strain
Stress
Courtesy: TA Instruments

52. Real Visco-Elastic Samples

53. DMA Viscoelastic Parameters: The Complex, Elastic, & Viscous Stress
The stress in a dynamic experiment is referred to as the complex stress *
The complex stress can be separated into two components:
1) An elastic stress in phase with the strain. ' = *cos
' is the degree to which material behaves like an elastic solid.
2) A viscous stress in phase with the strain rate. " = *sin
" is the degree to which material behaves like an ideal liquid.
Phase angle d
Complex Stress, *
* = ' + i"
Courtesy: TA Instruments
Strain, 

54. DMA Viscoelastic Parameters
The Complex Modulus: Measure of materials overall resistance to deformation.
G* = Stress*/Strain
G* = G’ + iG”
The Elastic (Storage) Modulus: Measure of elasticity of material. The ability of the material to store energy.
G' = (stress*/strain)cos
The Viscous (loss) Modulus:
The ability of the material to dissipate energy. Energy lost as heat.
G" = (stress*/strain)sin
Tan Delta:
Measure of material damping - such as vibration or sound damping.
Tan = G"/G'
Courtesy: TA Instruments

55. DMA Viscoelastic Parameters: Damping, tan 
Dynamic measurement represented as a vector
It can be seen here that G* = (G’2 +G”2)1/2
G"
Phase angle  G'
The tangent of the phase angle is the ratio of the loss modulus to the storage modulus.
tan  = G"/G'
"TAN DELTA" (tan )is a measure of the damping ability of the material.
Courtesy: TA Instruments

56. Frequency Sweep: Material Response
Transition
Region
Rubbery Plateau
Region
Terminal Region
Glassy Region
log G'and G" 1 2
Storage Modulus (E' or G')
Loss Modulus (E" or G")
log Frequency (rad/s or Hz)
Courtesy: TA Instruments

57. Viscoelasticity in Uncrosslinked, Amorphous Polymers
Logarithmic plots of G’ and G” against angular frequency for uncrosslinked poly(n-octyl methacrylate) at 100°C (above Tg), molecular weight 3.6x106.

58. Dynamic Characteristics of Rubber Compounds
Why do E’ and E” vary with frequency and temperature?
The extent to which a polymer chains can store/dissipate energy depends on the rate at which the chain can alter its conformation and its entanglements relative to the frequency of the load.
Terminal Zone:
Period of oscillation is so long that chains can snake through their entanglement constraints and completely rearrange their conformations
Plateau Zone:
Strain is accommodated by entropic changes to polymer segments between entanglements, providing good elastic response
Transition Zone:
The period of oscillation is becoming too short to allow for complete rearrangement of chain conformation. Enough mobility is present for substantial friction between chain segments.
Glassy Zone:
No configurational rearrangements occur within the period of oscillation. Stress response to a given strain is high (glass-like solid) and tand is on the order of 0.1

59. Dynamic Temperature Ramp or Step and Hold: Material Response
Glassy Region
Transition
Region
Rubbery Plateau
Region
Terminal Region
Log G' and G" 1
Loss Modulus (E" or G")
Storage Modulus (E' or G') 2
Temperature
Courtesy: TA Instruments

61. Blend

62. Epoxy

63. Nylon-6 as a function of humidity

64. E’storage modulus
Polylactic acid
E’’loss modulus

65. Tg 87 °C

66. Tg -123 °C (-190 F)
Tm 135 °C (275 F)

68. G’storage modulus
G’’loss modulus
These data show the difference between the behaviour of un-aged and aged samples of rubber, and were collected in shear mode on the DMTA at 1 Hz. The aged sample has a lower modulus than the un-aged, and is weaker. The loss peak is also much smaller for the aged sample.

69. Tan d of paint as it dries

70. Epoxy and epoxy with clay filler

73. Sample is strained (pulled, ) rapidly to pre-determined strain ()
Stress required to maintain this strain over time is measured at constant T
Stress decreases with time due to molecular relaxation processes
Relaxation modulus defined as:
Er(t) also a function of temperature
Er(t) = (t)/e0