RP Lecture 0

Polymer Rheology
P Sunthar
Department of Chemical Engineering Indian Institute of Technology, Bombay Mumbai 400076, India P.Sunthar@iitb.ac.in
05 Jan 2010
Introduction Phenomenology Modelling
Outline of the Lecture
P Sunthar (IIT Bombay)
Polymer Rheology
ComFlu 2009
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Nature of Polymeric Liquids Polymer Rheology
Outline of this Section
Introduction Nature of Polymeric Liquids Polymer Rheology Phenomenology Modelling
Polymer Rheology
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Questions to Ask for a New Phenomena

Fundamental Questions What makes the phenomena different ? How to represent in terms of a mathematical model ? Are there distinct laws or rules for the behaviour ? Are there other known phenomena that obey similar laws ? What role has this played in the current state of the universe ? Application oriented questions Can it be employed for betterment of quality of life? Consequences to processes that manipulate the material ?
Polymer Rheology
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Polymeric Liquids
Denition Liquids that contain Polymers Liquids: Materials that ow Simple Liquids
Denition: Material that does not support shear stress at rest
Complex uids
Liquid (viscous) and Solid (elastic) like behaviour Dynamic properties are not thermodynamic constants Eg: Viscosity = f ( ), = f (t).
Polymer Rheology
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Chemical Nature
Long chain monomers joined by chemical bonds Large molecular weights: 1000 to 109 Linear or branched Natural (DNA, Proteins) or Synthetic
Linear
Branched
Polymer Rheology
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Physical Nature
Linearity of large portions: L Flexibility: Not rigid long rods Is NOT: Suspension of polystyrene beads
Polymer Rheology
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States of Polymeric Liquids

Polymer Melts T > Tg . Eg HDPE Concentrated Solution Semi-dilute solution Dilute Solution, Eg: Polystyrene in cyclohexane
Polymer Melt
Concentrated Solution
Semi-Dilute Solution
Dilute Solution
Polymer Rheology
ComFlu 2009
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Role of Temperature
Noodle Soup What is the difference between a polymeric liquid to us and a huge bowl of noodles to a Giant? Noodles are linear, Soup is like a solvent. Difference Random linear translating motion Noodles is a zero temperature (Frozen) system Polymeric liquid is a nite temperature system
P Sunthar (IIT Bombay) Polymer Rheology ComFlu 2009 9 / 44
Role of Temperature
Role of Temperature
Role of Temperature
Need for Study of Polymeric Liquids

Polymer Processing
Reactors and Mixers Extrusion Moulding Films Fibre Spinning
Consumer Products
Shampoo Pastes Printing Inks Paints Lamination and Coating
Food Additives
Gums Glycerine
Polymer Rheology
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Nobel in Physics
Pierre-Gilles de Gennes \d -zhen\ 19322007 Nobel in Physics: 1991 Nobel for generalising theory of phase transitions to polymers and liquid crystals. Scaling Theory in Polymeric liquids Reptation in Polymer Melts Coil-stretch transitions in Extensional ows Polymer induced Turbulent drag reduction
Polymer Rheology
Industrial Flows are Complex
Geometry Polydisperse and Multi-component
Understand Response to Simple ows (Viscometric)

Shear Elongational
Understand Response of Simple Materials (reproducible)

Single or two component systems Monodisperse molecular weight Dilute Systems Melts (Pure polymer)
Rheology Science of Deformation and Flow

Polymer Rheology
Industrial Flows are Complex
Geometry Polydisperse and Multi-component
Understand Response to Simple ows (Viscometric)

Shear Elongational
Understand Response of Simple Materials (reproducible)

Single or two component systems Monodisperse molecular weight Dilute Systems Melts (Pure polymer)
Rheology Science of Deformation and Flow

Rheology Core: Viscosity and Elasticity

What is Deformation?
Relative displacements within material Measured by Deformation (Strain): Resisted by Elasticity xy G=
Deformation
Shear
Elongation
Flow
Shear
What is Flow?
Continuous Relative motion Measured by rate of Deformation (Strain rate): Resisted by viscosity =
Elongation
xy
Polymer Rheology ComFlu 2009 13 / 44
Polymers, Soft Matter, Complex Fluids

Liquid Water An Oil A polymer solution A polymer melt A glass Viscosity (Pa.s) 103 0.1 1 105 > 1015 Modulus G (Pa) 109 108 10 104 > 1010
Soft Materials Elasticity has Entropic Origin (Not Energetic origin as for solids) G proportional to kB T times number concentration of exible units Physical feel of softness, intermediate G Complex mechanical response and microstructure
Visual Linear Nonlinear
Introduction Phenomenology Visual Phenomena Linear viscoelasticity Nonlinear Phenomena Modelling
Polymer Rheology
ComFlu 2009
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Weissenberg Rod Climbing Effect

Rod rotating in a polymeric liquid Fluid climbs the rod Common uids that show
Gum solutions Batter (with egg white)
Due to Normal stress differences
psidot, Youtube: npZzlgKjs0I

Extrudate or Die Swell

POLYOXTM (PEO, PEG) Solution Ejected from a syringe Signicant increased diameter upon exit Also known as Barus Effect Newtonian uids diameter does not change signicantly Due to Normal stress differences
psidot, Youtube: KcNWLIpv8g

Tubeless Syphon
Elongational ow Stresses hold up against gravity and surface tension After initial pouring (suction) a free-surface syphon is maintained. Also known as Fano Flow
psidot, Youtube: aY7xiGQ-7iw

Drop Formation
Jet and Drop breakup Elongational ow Dilute PEO solution Elongational stresses hold against surface tension and gravity driven breakup Satellite drop
Polymer Rheology
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Turbulent Drag Reduction
Small amounts of polymers (ppm) to water Fluid drag in pipelines reduced signicantly Transportation of liquids.2 Fireghting: Farther throw
Polymer Rheology
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Contraction Flow
Sudden contraction low Re Flow Elongational ow Lip-vortices Corner Vortices

Polymeric Newtonian
Polymer Rheology
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Relaxation Times
Observable microscopic time scale, Simple liquids 1015 sec Time for large scale changes in polymer congurations Microseconds to minutes Similar order of macroscopic observation period and processing rates Congurations altered by thermal energy Elasticity is an Elastic time scale
Polymer Rheology
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Dimensionless Numbers
Macroscopic time scales Kinematic (rate of deformation) time scale
for shear ows for extensional ows
Weissenberg Number For Viscometric ows (with kinematic timescale) Wi = or (1)
Dynamic time scale, td

Time to traverse a geometry or section Pulsatile ow May not be known apriori
Deborah Number For complex ows (with dynamic timescale) De = td

ComFlu 2009
(2)
Polymer Rheology
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Molecular Weight Dependence of Relaxation Time
Large scale motion depends on M Scaling dependence for a class of liquids Class Dilute solution in poor solvent Dilute solution in -conditions Dilute solution in good solvent Semi dilute solution Entangled Melts Scaling M1.0 M1.5 M1.8 chain M2 rep M3.4
Polymer Rheology
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Linear Response
Response to small imposed deformation Linearity means additive response Linearity of Response in
Viscous properties Elastic properties
Linear Viscoelastic Properties Mainly Polymer physics Liquid Water An Oil A polymer solution A polymer melt A glass
Viscosity (Pa.s) 103 0.1 1 105 > 1015
Relaxation time (s) 1012 109 0.1 10 105
Modulus G (Pa) 109 108 10 104 > 1010

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Polymer Rheology
Rheological Tests
Oscillatory
Controlled Stress Controlled Strain
Stress Relaxation
After step strain After cessation of shear ow
Creep (Constant stress applied)
Polymer Rheology
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Zero-shear rate viscosity

Linear response ( 0) Micro-structural information Dilute: c < c Intrinsic Viscosity (inverse concentration) s [ ]0 lim [ ] lim lim 0 0 c0 c s [ ]0 M Semi-dilute: c <c< c
log sp0
Entangled
14/3
Semi Dilute 2 Dilute 1

c log c c
sp0 = 0 s Entangled: c > c

Small Amplitude Oscillatory Tests
G : Elastic Modulus; G : Viscous

Viscous Transition to Flow Rubbery/Plateau
log(G )
Glassy
G G 1 log()
log(G )
Polymer Rheology
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Plateau Modulus with Molecular Weight

Increased M Increased Entanglements Rubber like network Entanglements are like cross-links
Crosslinked Polymer
log(G )
log(G ) M
Entangled Melt
log()
G0 N
Unentangled Melt
log()
Polymer Rheology
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Characteristic Relaxation Time

Low Frequency response always Viscous G >G Wait long enough, even Mountains will ow! Low frequency scaling for all polymeric liquids (Maxwell model) G G 2 2 G 0 Cross over frequency or Characteristic relaxation time G G Zero-shear rate viscosity estimate = 0
G
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Polymer Rheology
Stress Relaxation
Small step strain is linear G(t) Fourier Transform G ( ) Small t large : Elastic Large t small : Viscous (ow) 0 = Area under the G(t) curve 0 G(0) for exponentially decaying tail: exp t/
log G(t) G0 N G (t )
G0 N
Response G(t) = xy /
Rouse
e rep
Reptation
Monomer
Rouse
0 log t
e rep
Reptation
Polymer Rheology
ComFlu 2009
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Shear Thinning
Decrease in viscosity upon shear More pronounced in concentrated solutions than dilute Intermediate shear rates: Power Law Fluid Worm-like Micelles Living Polymers abrupt changes
Cylindrical micelles Breaking and forming Large shear rates most are small fragments
log
4 Concentrated solution 2
Dilute Solution 0 Wormlike Micelle 2 5 1
log
Polymer Rheology
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Normal Stresses
Simple liquids: Normal stress is the pressure Complex uids: Microstructure leads to ow induced anisotropy Normal Stresses: N1 = xx yy N2 = yy zz Shear thinning for 1 = N1 / 2 N2 is usually 0 for polymeric liquids
log N1
N1
log ,
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Extensional Viscosity
Contraction ow Stagnation points Spinning of bres Break up of jets to drops Blow moulding
log + E
Stretching and Compressing ow eld
log t
Elongational viscosity E Experiments: Transient (not + Steady) E Tensile Stress Growth Coefcient Strain ( t) hardening
Polymer Rheology
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Trouton Ratio
Ratio of extensional to shear viscosity TR = E ( ) ( 3 )
log E
Solutions
E 3
Branched Melts Linear Melts
log
log ,
1000
log
Dilute Solution
Newtonian Liquids: TR = 3
log T R
100 Melts
3 Inelastic liquid
1/2 log ,
log
Polymer Rheology
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Solution Viscosity Normal Stresses Extensional Viscosity
Introduction Phenomenology Modelling Basics Shear Thinning Normal Stresses Extensional Viscosity
Polymer Rheology
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Dilute Solution and Colloidal Suspensions

Spherical particles only on the average Like Porous particles (uid can pass through) Suspension viscosity (Einstein) = s (1 + 2.5 ) Dilute polymer solution = s 1 + UR UR = 1.66 Zimm theory UR 1.5 Molecular simulations and Experiments
Tube Model
Chains cannot cross each other Entanglement is like a crosslink Motion between entanglements Pervaded volume: Tube [Sam Edwards, 1967] Primitive path
Entanglement Melt
Tube
Polymer Rheology
ComFlu 2009
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Reptation and other Relaxation Times

Smallest time 0 : Monomer relaxation Intermediate e : Rouse relaxation between entanglements Largest rep : Reptation or relaxation along the length of the tube [P G de Gennes, 1971] Diffusion time of polymer is reptation time
Monomer
Rouse Reptation
Polymer Rheology
ComFlu 2009
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Relaxation Modulus and Reptation
Relaxation after step strain Plateau region, relaxation between entaglements e Terminal region, reptation rep Viscosity related to reptation time 0 rep G(0)
log G(t) G0 N G (t )
G0 N
Initial monomer relaxation 0
Rouse
e rep
Reptation
Monomer
Rouse
0 log t
e rep
Reptation
Polymer Rheology
ComFlu 2009
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Shear Thinning in Melts
Entangled state (rubber like) high viscosity Entanglements are constraints for motion Shear ow releases some constraints High shear rate chains align along ow
Polymer Rheology
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Understanding Normal Stress Difference
Anisotropy in microstructure Equilibrium: spherical pervaded volume Shear Flow: Stretch and Tumble Shear pervaded volume: inclined ellipsoidal Restoring force in normal planes are different Normal stress difference
Shear yy xx Equilibrium
Polymer Rheology
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Extensional Viscosity in Dilute Solutions

Equilibrium: Spherical pervaded volume Small extension rates < 0.5, small deformation Large extension rates: stretching of chain, larger stress
Equilibrium
Small Extn.
Large Extn.
Polymer Rheology
ComFlu 2009
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Extensional Viscosity in Melts
Reptation
log E
Reptation
Orientation
Stretching
Tube orientation Rouse time: Chain Stretching

1 rep
log
1 e
Polymer Rheology
ComFlu 2009
Fully Stretched
Entanglements and Conning tube
44 / 44

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Polymer Rheology

Introduction Phenomenology Modelling

Outline of the Lecture

Introduction Phenomenology Modelling

P Sunthar (IIT Bombay)

Introduction Phenomenology Modelling

Nature of Polymeric Liquids Polymer Rheology

Outline of this Section

Introduction Nature of Polymeric Liquids Polymer Rheology Phenomenology Modelling

P Sunthar (IIT Bombay)

Introduction Phenomenology Modelling

Nature of Polymeric Liquids Polymer Rheology

Questions to Ask for a New Phenomena

P Sunthar (IIT Bombay)

Introduction Phenomenology Modelling

Nature of Polymeric Liquids Polymer Rheology

P Sunthar (IIT Bombay)

Introduction Phenomenology Modelling

Nature of Polymeric Liquids Polymer Rheology

P Sunthar (IIT Bombay)

Introduction Phenomenology Modelling

Nature of Polymeric Liquids Polymer Rheology

P Sunthar (IIT Bombay)

Introduction Phenomenology Modelling

Nature of Polymeric Liquids Polymer Rheology

States of Polymeric Liquids

P Sunthar (IIT Bombay)

Introduction Phenomenology Modelling

Nature of Polymeric Liquids Polymer Rheology

Introduction Phenomenology Modelling

Nature of Polymeric Liquids Polymer Rheology

Introduction Phenomenology Modelling

Nature of Polymeric Liquids Polymer Rheology

Introduction Phenomenology Modelling

Nature of Polymeric Liquids Polymer Rheology

Introduction Phenomenology Modelling

Nature of Polymeric Liquids Polymer Rheology

Need for Study of Polymeric Liquids

P Sunthar (IIT Bombay)

Introduction Phenomenology Modelling

Nature of Polymeric Liquids Polymer Rheology

Introduction Phenomenology Modelling

Nature of Polymeric Liquids Polymer Rheology

Understand Response to Simple ows (Viscometric)

Understand Response of Simple Materials (reproducible)

Rheology Science of Deformation and Flow

Introduction Phenomenology Modelling

Nature of Polymeric Liquids Polymer Rheology

Understand Response to Simple ows (Viscometric)

Understand Response of Simple Materials (reproducible)

Rheology Science of Deformation and Flow

Introduction Phenomenology Modelling

Nature of Polymeric Liquids Polymer Rheology

Rheology Core: Viscosity and Elasticity

Introduction Phenomenology Modelling

Nature of Polymeric Liquids Polymer Rheology

Polymers, Soft Matter, Complex Fluids

Introduction Phenomenology Modelling

Visual Linear Nonlinear

Outline of this Section

Introduction Phenomenology Visual Phenomena Linear viscoelasticity Nonlinear Phenomena Modelling

P Sunthar (IIT Bombay)

Introduction Phenomenology Modelling