POLYMER PROCESSING Dr Wan Zaireen Nisa Yahya

CEB4423 Email: [email protected]

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Office: 05-3687584 ( 04-03-24)
CEB 4423
Polymer
processing
Chapter 8:
Rheology

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 1. Introduction to rheology

2. Polymer melt rheology

• Polymer melt viscosity

Contents • The WLF Constants

• The molecular weight Dependence of the

Melt viscosity

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Lesson Outcome

At the end of this lecture, students should be able to

• describe the rheology
• evaluate the viscosity and temperature dependence
• evaluate the viscosity and molecular weight
dependence

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1. Introduction to rheology

Definition of Rheology:
• Study of deformation and flow of matter which describes the
interrelation between force, deformation and time

• A fluid is a substance that deforms continuously under the action of a

shearing force.
• Intuitively, a fluid flows!

• Inquiry into the flow behavior of complex fluids

• Complex fluids do not follow Newton’s Law or Hooke’s Law (of elasticity)

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 1. Introduction to rheology
Newton and Simple Fluids
Reflected upon the resistance of liquids to a cylinder rotating in a vessel.

Newton(-Stokes) Law

Deformation rate, ϒ is expected to be proportional to stress, τ and the

constant coefficient of proportionality is called viscosity, η.

For Newtonian fluid: τ = ηγ 𝜎𝜎 = 𝜂𝜂

𝜕𝜕𝛾𝛾
𝜕𝜕𝑡𝑡

The study of simpler fluids have their own well-defined field, called fluid

mechanics.

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 1. Introduction to rheology
What is Rheology Anyway?
An answer for your baffled family and friends.
• “Rheology is the study of the flow of materials that behave in an interesting
or unusual manner. Oil and water flow in familiar, normal ways, whereas
mayonnaise, peanut butter, chocolate, bread dough, and silly putty flow in
complex and unusual ways. In rheology, we study the flows of unusual
materials.”
• “… all normal or Newtonian fluids (air, water, oil, honey) follow the same
scientific laws. On the other hand, there are also fluids that do not follow
the Newtonian flow laws. These non-Newtonian fluids, for example mayo,
paint, molten plastics, foams, clays, and many other fluids, behave in a wide
variety of ways. The science of studying these types of unusual materials is
called rheology”

*Faith Morrison, “The News and Information Publication of The Society of Rheology”, Vol 73(1) Jan 2004, pp 8-10
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1. Introduction to rheology
World’s Longest Running Laboratory
Experiment – The Pitch Drop Experiment
 1927 – Prof Parnell in Univ. of Queensland
Australia heated a sample of pitch (like bitumen)
and poured it into a glass funnel with a sealed
stem. Three years were allowed for it to settle,
after which the stem was cut.
 Examine the viscosity of the pitch by the speed
at which it flows from a funnel into a jar.
 Only eight drops has fallen in 80 years.
 The viscosity is approximated as 100 billion times
that of water.

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Viscosities of some common materials
Composition Viscosity, Pa·s Consistency
Air 10-5 Gaseous
Water 10-3 Fluid
Polymer latexes 10-2 Fluid

Olive oil 10-1 Liquid

Glycerine 100 Liquid

Golden syrup 102 Thick liquid
Polymer melts 102 -106 Toffee like
Pitch 109 Stiff
Plastics 1012 Glassy
Glass 1021 Rigid

Viscosity of water = 1 cPoise / 1cP = 1 mPa·s 9

1. Introduction to rheology

Flow
• Flow is the continuous deformation under an influenced of constant
force

• Any particle of materials will not back to the original positions after
the force of deformation been released

• All the body in the nature will flow if given a period of time and
appropriate temperature even with very low applied force

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 1. Introduction to rheology

Flow

• Ability to flow for a molten materials depends on

the molecular chain mobility that hold molecule
together.
• Low mobility with high degree of chain entanglement
 will influenced the ability to flow and the process
ability of polymeric materials

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Shear viscosity

• Shear viscosity is a measure of the internal resistance of the fluid

against and applied shear force
• In many polymer processes, the shear viscosity is the most important
material variables controlling the process
τ
η = .
γ
η - shear viscosity
τ - shear stress
.
γ - shear rate

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Shear Viscosity

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Viscosity
 The unit of viscositiy was poise, P, or centipoise, cP.
1 mPa·s = 1 cP
 η rapidly decreases as temperature increases.
 Ideal fluids are called Newtonian. The viscosity is independent
of the rate of shear

Shear rate is a measure of the rate

of shear deformation

Rheogram for Newtonian liquids.

A - high viscosity, B - low viscosity.

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Newtonian Liquid
 Newtonian liquid, where shear stress is proportional to shear rate,
with the proportionality constant being the viscosity
 A Newtonian fluid (named for Isaac Newton) is a fluid that flows like
water
 For example, water is Newtonian, because it continues to exemplify
fluid properties no matter how fast it is stirred or mixed.
 If the liquid is not Newtonian, a plot of shear vs. the rate of shear is
not a straight line but a curve

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 Non- newtonian flow

 Most of the polymer systems DO NOT FOLLOW

Newtonian law.

 Non Newtonian flow can be classified into:

1. Non time dependence flow

2. Time dependence flow

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 Non time dependence flow
 Shear rate for non time dependence flow and the shear stress can be
represented mathematically as:
γ = f (τ )
 In rheological studies there are 4 types of flow that not dependence
with time ;
1. Bingham body flow,

2. Pseudoplastic flow,

3. Newtonian flow

4. Dilatant flow

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Shear rate Vs flow for non time dependence flow

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 Pseudoplastic flow
Or Shear thinning

 Viscosity of pseudoplastic flow decreased with the increased in

shear rate  it showed the shear thinning behaviour
 During real processing that involved a higher range of shear rate
 no problems of flowing for pseudoplastic materials
 At suppressed condition  molecule has higher entanglement
and will have random conformation or orientation
 Under the applications of shear force  uncoiled of molecule
chain occur and the orientation of molecule increased even
though the occurrence of Brownian movement will try to gives
the original conformation (the condition where no force
occurred)
 At very high shear rate  the almost Newtonian behaviour was
observed for materials with pseudoplastic flows
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 Shear Thinning

• shear thinning – tendency of some materials to decrease in viscosity

when driven to flow at high shear rates, such as by higher pressure
drops

Increasing shear rate

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Pseudoplastic

 Pseudoplastic, or shear-thinning fluids have a lower

apparent viscosity at higher shear rates.

Non-Newtonian
Newtonian
•
Shear stress τ (τ , γ)

Tan-1µa
γ Shear rate

The apparent viscosity at ((τ, γ) is µa = τ / γ ; µa decreases

with increasing γ .

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Pseudoplastic

 The conditions in processing equipment are

adjusted to make full use of this large order of
magnitude reduction in apparent shear viscosity
with increasing stress.

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 Dilatant Flow
Shear Thickening
 Viscosity value for Dilatant flow increased with increasing
shear rate
 polymer to be processed at high shear rate due to the
ability to flow polymer is low.

 Dilatant behaviour normally shown by polymer with high

suspension such as PVC and materials with non uniform
particles shape
 materials that are difficult to be compressed under high
shear rate.

 Dilatant behaviour is hardly shown for molten polymer

except under a special condition  where the melt
crystallization occurred during flow.
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Dilatant
 A dilatant material is one in which viscosity increases with the
rate of shear (also termed shear thickening).
 The dilatant effect can be seen more readily with a mixture of
corn starch and water

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 Shear Thickening

• shear thickening – tendency of some materials to increase

in viscosity when driven to flow at high shear rates

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 Body Bingham flow
 Body Bingham is elastic solid  ideal materials that their
structure will collapse when the stress applied greater than
their yield stress τy,
 Shear stress for body Bingham are proportional with shear
rate given as:
τ = ηγ + τ y
 Materials that represents model Bingham  including
emulsion and suspension with high concentration such as
paint, printing ink, clay slurry and plastic emulsion.

 Examples of “ideal” yield stress fluids

• Nivea Lotion ~ 4 Pa
• Gilette foamy shaving cream ~10 Pa
• Aloe gel ~60 Pa
• Nivea Cream, Toothpaste and Mayo ~200-300 Pa 27
 Influenced of temperature on viscosity

 Understanding the influenced of temperature with

the melt viscosity is importance in:
 Polymer processing
 To estimate the thermal resistance of particular
materials
 Big variation in viscosity with range of temperature
 represent the materials need a higher activation
energy
 polymer molten viscosity that depends on
temperature have a higher temperature from glass
transition temperature Tg or their melting
temperature Tm.
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 The Arrhenius equations can relate the activation
energy during chain mobility as

 ∆Ea 
 
η=A  RT 

Where η= viscosity of polymer melt

Ea = activation energy
R = Universal gas constant
T = Temperature (°K)
A = Arrhenius constant

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 When taking the logarithm plot from log η against log (1/T)
will given one straight line where the slope is the same
activation energy according to this equations:

 ∆E a  1 
Log η =   
 RT  T 
 If viscosity at various temperature taken at constant shear stress
 activation energy is supposed to be constant and not
dependence on shear stress where it been taken.
 If the viscosity at constant temperature at various shear rate 
activation energy dependence on shear rate
 example activation energy decreased with increasing shear
rate
 However the flow according to Arrhenius equations activation
energy almost not dependence on temperature.

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Viscometers
These are employed to measure viscosity:
 Capillary viscometer
 Rotational rheometer
 Simple shear viscometer
 Cone & plate rheometer
 Parallel plate viscometer
 Tensile & extensional viscometer

Schematic diagram of a cone and plate viscometer.

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Schematic diagram of a rotational viscometer
Polymer Melt Rheology
Molecular Structure and
Processing
Rheology as a Tool for Polymer Development
Rheology, Structure and Processing
 Extrudate Swell – Elastic Effect

Left – Newtonian liquid (silicone fluid),

Right – Concentrated solution of 2.44g
Polymethyl methacrylate in 100 ml of dimethyl phtalate.
Elastic and Viscoelastic Effects
 Weissenberg Effect (Rod Climbing Effect)
 does not flow outward when stirred at high speeds

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 Chain Branching

Long Chain
Branching
(LCB)

Short Chain
Branching (SCB)
Type of Flow
Laminar to Turbulence
Shear Rates in Various Processing Technique
Shear Viscosity and Molecular Weight
Distribution (MWD)
Shear Thinning and Long Chain Branching (LCB)
 Mw and Shear Viscosity

Mw Viscosity
Temperature and Shear Viscosity
Activation Energy for Viscous Flow
LCB and Activation Energy for Viscous Flow

G’ Shear modulus
POLYMER MELT VISCOSITY

WLF Equation (Williams-Landel-Ferry)

• In the Modulus-temperature curve, linear amorphous
polymer are capable to flow if they are subjected to a shear
stress. The flow behaviour of polymers always contains some
elements of viscoelasticity.
 Table 1 WLF parameters

Polymer

Polyisobutylene 16.6 104 202

Natural rubber (Hevea) 16.7 53.6 200

Polyurethane elastomer 15.6 32.6 238

Polystyrene 14.5 50.4 373

Poly(ethyl methacrylate) 17.6 65.5 335

“Universal constants” 17.4 51.6

Chain length and viscosity

𝑍𝑍𝑊𝑊 = chain length

2∗𝑀𝑀𝑤𝑤
𝑍𝑍𝑊𝑊 =
𝑍𝑍𝑐𝑐𝑤𝑤 𝑀𝑀0
With 𝑀𝑀0 =molecular
weightof monomer
𝑀𝑀𝑊𝑊 =molecular weight of
polymer

𝑍𝑍𝑐𝑐𝑐𝑐 = critical
engtanglement
chain length
𝑍𝑍𝑐𝑐𝑤𝑤
 𝑍𝑍𝑐𝑐,𝑤𝑤 = critical engtanglement chain length Z c,w = 600

EXAMPLE 1
 Summary

In rheological studies there are 4 types of flow that are not
dependence with time : Bingham body flow, Pseudoplastic
flow, Newtonian flow and dilatant flow

Dependence between chain length Zw and melt viscosity:

η = 𝐾𝐾𝐿𝐿 ∗ 𝑍𝑍𝑤𝑤 𝑖𝑖𝑖𝑖 𝑍𝑍𝑤𝑤 < 600 η = 𝐾𝐾𝐻𝐻 ∗ 𝑍𝑍𝑤𝑤 3.4 𝑖𝑖𝑖𝑖 𝑍𝑍𝑤𝑤 >
600

Dependence between melt viscosity and temperature: