Instructor: Dr.

Zubair Khaliq
Assistant Professor
(Department of Polymer Engineering)
 What is Rheology ??

“Everything Flows”

“The mountains flowed before the Lord.” M. Reiner said.

Overview of the Class
• Fields of Rheology
1. Rheology for theory advancement
Development of new rheometer
2) Rheology for process design
Prediction of elastic turbulent (or melt fracture)
Information on mold design, etc
3) Rheology for material characterization
Relative evaluation of molecular parameters
Information on polymerization process, etc.

*** This class focuses on fields 2 and 3

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What is rheology ??
❑Rheology is the study of flow and deformation of materials,
which come from viscoelasticity.
✓Deformation is either reversible or irreversible.
✓Reversible one leads to time-independent (instantaneous) elastic
response, which results in elastic recovery.
✓Irreversible one leads to time- dependent viscous response, which results
in flow.
❑Thus, rheology is a study of the flow of materials which
simultaneously produce irreversible and reversible
deformations on applying stress.

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 What is rheology ??

❑Rheology deals with viscoelastic material whose flow

accompanies both reversible and irreversible deformation on
deformation

✓Irreversible deformation results from molecular slip (viscous properties)

✓Reversible deformation results from network structure formed by “retained”

entanglement and crosslinking (elastic properties)

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What is rheology ??

The first target of rheology is to analyze the flow properties of

polymers

Origin of Physical Properties of Polymers

Polymer Chain
In fact, polymers have extremely small sizes
10-6 to 10-3 cm in chain length
n

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Historical Background

❑In 1920s – 1930s

❑Physical aggregation vs. covalent bonding for polymers
❑One decade’s dispute based on the cellobiose (Physical
aggregation)
From 1940s
❑Covalent bonding concept based on nylon 66 (Carothers
DuPont)

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Historical Background

1960s – 1970s
❑Molecular entanglement concept by W. W. Graessley
❑[ref.] Advances in polymer science

From 1980s
• Topological constrains concept (Not permanent entanglement but
temporary networking)

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Historical Background

Mechanical Properties
Combined responses of physical aggregation and
molecular entanglement to a given stress

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Mechanical Properties Combined responses of physical
aggregation and molecular entanglement to a given stress

Crystallization Orientation
Crystalline
❑Regular lattice structure ❑Just ordered

❑Thermodynamic ❑Kinetic
Amorphous
❑Melting endotherm ❑Baseline shift only

❑The most stable state ❑Meta-stable

❑Isotropic properties ❑Anisotropic

Polymer chains
arrangement
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Physical Properties of polymers depend upon

❑MW & MWD : Low MW molecules increases the frequency of

chains ends (high mobility) and play the role of plasticizer (or
lubricant)
❑Intermolecular interactions: Crystalline, Oriented and
Amorphous Regions
✓MW, MWD and Architecture
✓Chain stiffness & polarity
❑UHMWPET (nonpolar) vs. Kevlar (polar, rigid domain)
❑PET vs. polyamide 66

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4. “Apparent MW” Concept

❑ Strong intermolecular interactions enlarge the effect of

molecular weight, the apparent MW has dominant effect
on mechanical properties. Ex. Ionomers
❑ PE vs. iPP: Crystallinity
❑ PE vs. Nylon 66: intermolecular interaction through
hydrogen bonding

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 Rheology vs. Physics

❑Large deformation Small

deformation Ex. Stress-strain
curve of polymers

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Parameters
• Processing; T, P, deformation level & rate
• Materials; MW, MWD, Architecture (branching, crosslinking)
Crosslinking
Stress

Stress
Stretching rate Molecular Weight

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Strain Polymer Rheology and Viscoelasticity
Strain 14
Nature’s Law

❑Any system try to increase its entropy

• The universe is expanding
❑Any systems try to decrease its surface
• Drops of water or oils
❑Higher rate of deformation brings about more elastic response
• Fast falling raindrops
• S-S curve of polymeric material

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5. Physics & Rheology

❑External stimuli
• Cause
• Material
• Responses (Result)
❑To give diverse stimuli (temperature, pressure, light, stress and
their controlled mode) is the key to understand the material
[Experimental design = Creativity]

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Rheology relates strain (response) to
stress (stimuli)
❑Diverse mode of stressing is the key to understand the
response of the material
❑Experimental design = Creativity
• Strain rate sweep
• Time sweep
• Step stressing
• Loop stressing, etc

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Important Definitions
1. Scalar vs. Vector
Speed vs. Velocity
Area vs. Surface
i. Force: A vector (first tensor with 3
components in 3-D space)
ii. Surface: A unit vector normal to the
plane
• Any element of a surface can be
expressed as the sum of 3 components
in3-D space, each component having a ii. If not equal, shear stresses resulting
normal vector parallel to one of the
coordinate axes
• A given surface area component is
identified with the coordinate direction of
its normal vector.
2. Stress: (σij) = force/area
i refers to the plane on which the stress acts
and j represents the direction of the stress
• A second-order tensor: 9 combinations of 3
force elements acting on 3 surface
components at a given point
i. If i=j, normal (or tensile) stresses,
resulting in extensional (or
stretching) flow
in shear flow

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 Important Definitions

• Strain (Ԑij) : A quantitative

• Tensile stress measure of deformation
• Σ = stretching force / cross-sectional • Deformation: The displacement of a
area point relative to adjacent points
(not absolute)
• Shear stress
• τ = shear force / tangential area • Tensile strain : Linear deformation
in simple extension
Ԑ = (L – L0) / L0

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 Important Definitions

• Shear strain : displacement / • Stressed and strained

distance between plates • Stressed : balanced forces
ɣ = ΔX / h (∑F = 0) : No change in translation or
rational component of motion
• Shear rate (ɣ) = rate of change of • Strained : Deformation on applying
shear strain with time (sec-1) the balanced forces if the body is
ɣ = dɣ/dt = (1/h)(dΔX/dt) = V/h not liquid
• Viscosity : Resistance to flow of • Modulus : Resistance to
viscous fluids deformation of elastic bodies
• Newtonian liquid • Hookean solid
• Tensile and shear modulus
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7. Schematics of tensile and shear
deformation
• Extensional = elongation = stretching = tensile --- disentanglement = uncoiling (?)
• Shear --- rotation --- entanglement = coiling (?)

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Deformation mode of polymer chains under stress

Rotation (coiling with orientation of localized chains) of chains is

dominant in the shear field and alignment (stretching orientation of
whole chains) of chains is dominant in the tensile flow field
ef. The rotational action is more dominant at higher shear rate

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Deformation mode of polymer chains under stress

Figure 1: Action of flow fields on coil molecules.

Top: Shear flow. The shear gradient (I) generates principal stresses (II). The gradient forces the
molecule to expand in the direction of the main principal stress (III). The gradient forces the molecule
to rotate (IV), allowing it to return to the macro-conformation of a random coil. See also Figure 2.
Bottom: Tensile flow. The drawing action reduces the cross-sectional area of the specimen (I).
Principal stresses (II) force the molecule to expand in the direction of the main principal stress (III). On
further drawing, the molecule becomes completely stretched (IV).
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 Objective of Rheology
To measure (or to calculate) the variation of vicosity and elasticity
with shear rate (so-called Material functions) for polymeric
materials as a function of shear rate.
*The basic principles of rheometers are called rheometry.
1) Assumptions of Rheometry
i. Laminar, steady-state and non-wallslip viscometric flow
ii. Incompressible , homogeneous, and isotropic continuum

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 Objective of Rheology
2) Material functions (variation of viscosity and elasticity versus
shear rate or frequency) are measured by rheometers to define
the viscoelastic properties of polymeric materials in a
quantitative way.
i. Viscosity functions
τ12 = η(ɣ)ɣ, in which ɣ is shear rate
ii. Elasticity functions
N1 = τ11 - τ22 = φ1(ɣ)ɣ2, and
N2 = τ22 – τ33 = φ2(ɣ)ɣ2
In which, N1 and N2 are first and second normal stress difference functions,
respectively.

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Schematic viscosity and first normal stress
difference (N1) curves of polymers
2 figures
❑ Practical Importance
i. Viscosity : power supply,
polymer blend conditions,
ii. N1 : mold design, maximum
production rate, elastic
turbulence
Rheology tries to derive the
relation between stress and
strain

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Ref. Elasticity in the solid molten state

Polystyrene •Greater N1
(PS)

High Impact •Higher elasticity

PS
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