Polymer Flow

Introduction
● The complex flow (rheological) properties of polymeric melts play a
dominant role in shaping operations.
● Rheology is the study of the response of fluids (and solids as well) to applied
stresses.
● Also as large macromolecules are more often to get entangled, implies their
is high resistance to shear force. This in turn means high viscosity.
● High viscosity makes it a requirement to have robust pumping equipment.
● Note: High shear force causes mechanical molecular degradation (rupture of
covalent bonds).

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 NATURE OF POLYMER FLOW
Weissenberg Effect
The Weissenberg effect is a phenomenon that occurs
when a spinning rod is inserted into a solution of
elastic liquid. Instead of being thrown outward, the
solution is drawn towards the rod and rises up
around it. This is a direct consequence of the normal
stress that acts like a hoop stress around the rod.

https://en.wikipedia.org/wiki/Weissenberg_effect
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 NATURE OF POLYMER FLOW
Extrudate Swell
Die swell occurs in instances of polymer extrusion,
in which a stream of polymeric material is forced
through a die, a specialized tool in manufacturing to
shape or cut polymeric materials. Die swell is an
instance where a polymer stream is compressed by
entrance into a die, and is followed by a partial
recovery or “swell” back to the former shape and
volume of the polymer after exiting the die, hence
the term die swell.

https://en.wikipedia.org/wiki/Die_swell#:~:text=Die%20swell%2C%20also%20known%20as,shape%20or%20cut%20
polymeric%20materials.
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Nature of Polymer Flow
● The cause of these unusual behaviour is ELASTICITY (in the liquid state)
● Polymers are viscoelastic materials.
● Where viscoelasticity is the property of materials that exhibit both viscous
and elastic characteristics when undergoing deformation.

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 Ideal Behaviour
● For Rigid solid we get no deformation
● For Elastic solid(Hooke’s Law followed), i.e., linear deformation (no yield, no
creep and recovers completely).
● Whereas for, Newtonian Liquids: direct (linear) proportionality between
applied stress and rate of strain.

Shear Stress

Strain Rate
τ=n४ (Shear Rate) τ=F/A=-nv/H=-n४ (n: viscosity) 6
Power Law Model
● τ=m४n
● Where m is consistency while n is flow index.
● Polymer melts behave as Newtonian liquids at very low and very high strain
rates
● In the strain rate range important in processing they obey the Power law
Model.
● Power Law Model is advantageous in a sense that the parameters are easy to
calculate.
● But as a drawback, Dimension of m depends on the magnitude of n and It
predicts higher viscosity at lower strain rates.

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Carreau Model

● ηо : Zero Shear Viscosity

● η∞ : Zero Shear Viscosity at infinite shear rate
● λ : Time constant
● n : flow index
● Carreau Model describes well the very low and very high shear rate
behaviour and the constants have physical meaning.
● But, non-linear even in the parameters so needs numerical iteration
methods
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Common Shear Rate Values in Polymer Processing

Processing Shear rate (1/s)

Compression Molding 1 to 10

Calendering 10 to 100

Extrusion 100 to 1000

Injection Molding 1000 to 10000

Fiber Spinning >10000

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Time Dependent Flow Behaviour
● Thixotropy: viscosity decrease in time at constant shear rate (eg. paints,
gelcoat)
● Rheopexy (or anti-thixotropy): viscosity increase in time at constant shear
rate (eg. lubricants)
● All this due to change in structure as a result of applied strain (shear rate).
● After stopping the shearing the structure is rebuilt.

Thixotropy Rheopexy

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X-axis: Time; Y-axis: Viscosity
Effect of Molecular Weight on Viscosity

● ηо=kMw3.4 (after Mc)

● Increase in Molecular Weight implies
more entanglements
● More Entanglements will lead to higher
resistance to shearing
● Higher resistance to shearing means
higher viscosity
● So according to the equation given,
doubling Mw will increase η by 10 times

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Effect of Temperature on Viscosity
● In general, increasing temperature decreases viscosity
● The temperature sensitivity of various polymers can differ considerably.
● Arrhenius Equation:

η=AeE/RT

● Where, A : material constant, E: activation energy of flow, R: gas constant

(8.314 J/mol K), T: (absolute) temperature
● WLF Equation:

● αT(T): shift factor, C1, C2: material constants, T0 : reference temperature

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Effect of Pressure on Viscosity
● As pressure increases, the molecules come closer which implies the friction
increases between them which leads for viscosity to increase
● ηp =ηo exp(αp.p), where αp is pressure dependence coefficient

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Steady State Flow in a Tube

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Assumptions
● The flow is laminar, the inertia forces are low (can be neglected) compared to
the shear forces
● The flow is isothermal (temperature is homogeneous)
● The flow channel is fully filled with the melt
● The melt is incompressible
● Gravity forces can be neglected
● The flow is one-dimensional
● Flow channel end effects (entrance/exit) can be neglected
● The no-slip condition (at the channel wall) holds

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Force Balance
ΣFz = 0 = F1 + F2 + F3

F1 = π r2 P

F2 = -π r2 [P + (∂P/∂z)dz]

F3 = 2πrτrzdz

Shear Stress Distribution:

τrz=(r/2)(∂P/∂z)=(r/2)(PL-P0)/L=rΔP/2L

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For Newtonian Fluid

● As, τ=n४
● Implies, τrz=n(∂vz/∂r)

vz= (1/4n)(ΔP/L)(R2-r2)=(1/4n)(ΔP/L)[1-(r/R)2]

● By integrating over the tube cross section:

Q= ∫R02πrvzdr=∫R02πr(1/4n)(ΔP/L)(R2-r2)dr

=πR4ΔP/8nL(Hagen-Poiseuille Equation)

Where Q=volumetric flow rate

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For Power Law Fluid
● τ=m४n
● So by similar steps like before we get,

vz=(n/n+1)(ΔP/2mL)1/nRn+1/n[1-(r/R)n+1/n]

● Also volumetric flow rate, Q, is

Q=(nπR3/1+3n)[RΔP/2mL]1/n

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Thank You!!

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