Rheology 101

Nov 2011

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Presentation plan

Theoretical concept
− Viscoelasticity
− Flow behavior
Apparatus / measurements
Thermo mechanical analysis
– Detailed description
Rheology models

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Presentation plan

Theoretical concept
− Viscoelasticity
− Flow behavior
Apparatus / measurements
Thermo mechanical analysis
– Detailed description
Rheology models

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Theoretical concept

Objectives/Expectations:
What is Rheology ?
Why do Rheology ?
What is a Rheometer ?
What do stress & strain mean ?
What is visco-elasticity ?

Other questions ?

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Theoretical concept

What is Rheology

Rheology ( /riː
ɒlədʒi/) is the study of the flow of matter: primarily in the liquid
state, but also as 'soft solids' or solids under conditions in which they respond
with plastic flow rather than deforming elastically in response to an applied
force.[1] It applies to substances which have a complex molecular structure, such
as muds, sludges, suspensions, polymers and other glass formers (e.g. silicates),
as well as many foods and additives, bodily fluids (e.g. blood) and other biological
materials.

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Theoretical concept

Why do Rheology ?

• Petrol
• Formulation
• Cosmetic, medical
• Characterization
• Food
• Quality control
• Paint & coating
• Process optimization
• Polymers
• Upstream work
• Concrete
• Adhesives

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 Theoretical concept

What is a rheometer ?

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Theoretical concept

What do stress & strain mean ?

Relax

Shear Elongation
Surface S F F F

h l0 Surface S
l
x
x
γ = F l − l0 F
h τ= ε= τ=
S l0 S

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Theoretical concept

What do stress & strain mean ?

Viscosity is a measure of the resistance of a fluid which is being deformed by

either shear stress or tensile stress. It describes a fluid's internal resistance to
flow and may be thought of as a measure of fluid friction.
τcis τel
ηcis = ηel =
γ& ε&
Product Viscosity in Pa.s
Air 18.5.10-6
Water 1.10-3
Oil (for food) 84.10-3
Cream (cosmetics) 1 to 100
Paint 10 to 1000
Resin, bitumen 100 to 100 000
Granit 1020

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 Theoretical concept

What is visco-elasticity ?

X τ γ

F = kX
Comportement élastique :
La force est proportionnelle
au déplacement t
t

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Theoretical concept

What is visco-elasticity ?

X γ
F = ηV = ηX& τ
Comportement visqueux :
La force est proportionnelle
à la vitesse de déplacement

t t

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Theoretical concept

What is visco-elasticity ?

τ
F F
X X

γ t
γ γ

+ =
t t t

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 Theoretical concept

γ
τ
E
γ t t
V
t γ t t
VE
t t

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Theoretical concept

What is visco-elasticity ?

Maxwell Liquid. Kelvin-Voigt Solid

t J(t) t J(t)
1/η
J J
t J η t
η
t g t
g
Viscous liquid with an This solid contains a delayed
instantaneous elastic behavior elasticity in comparison with Hook
solid

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Presentation plan

Theoretical concept
− Viscoelasticity
− Flow behavior
Apparatus / measurements
Thermo mechanical analysis
– Detailed description
Rheology models

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 Theoretical concept

Shear thickening
Log (η)
Newtonian

Shear thinning
Log(γ& )

Testing conditions need to be provided

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Theoretical concept

Yield material

Shear thinning
Newtonian
Shear thickening

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Theoretical concept

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Presentation plan

Theoretical concept
− Viscoelasticity
− Flow behavior
Apparatus / measurements
Thermo mechanical analysis
– Detailed description
Rheology models

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Apparatus / measurements

What is a rheometer ?

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Apparatus / measurements

Dynamical rheometer Dynamical rheometer

Capillary rheometer (stress controled) (strain controled)

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 Apparatus / measurements

10000
PEbdl
PEhd
PEbd

PEbd
η (Pa.s)
1000
PEhd

PEbdl

Capillary rheometer

100
10 100 1000
TauxShear rate (s-1)
de cisaillement

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Apparatus / measurements
Modulus

G”

G’

Temperature
Modulus

Dynamical rheometer G”
(strain controled)
G’

Frenquency

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Apparatus / measurements
Modulus

G”

G’

Temperature
Frequency

Strain

Dynamical rheometer
(stress controled)

Time

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 Theoretical concept

γ
τ
E
γ t t
V
t γ t t
VE
t t

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Apparatus / measurements

γA
τA γ
Principle of measurement : τ
t

The strain g is defined by : γ = γ0.sin ωt

with ω = 2p/f 1/f
δ/2πf

The measured Stress is τ = τ0.sin( ωt+δ δ) where d is the damping factor

It could be also : τ = τ0.sin ωt.cos δ + t0.cos ωt.sin δ

From the latest formula we can extract 2 values

τ0 τ0
G' = . cos δ G'' = . sin δ
γ0 γ0
Storage modulus Loss modulus

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Apparatus / measurements

Which geometry ?

Couette cylinders Plate/plate or cone/plate Torsion

Liquid/fluid Past/elastic Solid

Viscosity

Tank behavior application behavior Adhesive joint

behavior
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 Presentation plan

Theoretical concept
− Viscoelasticity
− Flow behavior
Apparatus / measurements
Thermo mechanical analysis
– Detailed description
Rheology models

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Thermo mechanical analysis

Torque measured
Modulus

G”
Heating/
cooling
G’
system
Temperature
Strain applied Application temperature
Temperature

Temperature decreases

equilibrium Time

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T-Scan Highlights

Modulus G’
Tan delta
(log-scale)

G”
G’ @ 25°C
G’ @ 50°C

Tan delta
1
Mini Valley
Temperature
Tg Tx
Tx : Softening point
Mini Valley : Cohesion
G’ @ 50°C : Modulus at high temperature
G’ @ 25°C : behavior at Room temperature
Tg : glass transition

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Presentation plan

Theoretical concept
− Viscoelasticity
− Flow behavior
Apparatus / measurements
Thermo mechanical analysis
– Detailed description
Rheology models

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Rheology models : Structure – properties relationship

G’’

G’

Styrene bloc copolymer typical rheological profile

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Rheology models : Structure – properties relationship

G’’

G’

Polyolefin typical rheological profile

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 Rheology models

de Gennes / Doi-
Doi-Edwards Models

4 relaxation domains

C C
C
Me Mw

Glass transition Mvt Rouse

Mvt reptation
G ( t ) = Ghf ( t ) + G A ( t ) + GB ( t ) + G C ( t )

Local relaxation De Gennes/Doi-Edwards

τ HF ∝ M 0 τA ∝ M 0 τB ∝ M 2 τ ∝ M 3− 4
C

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Rheology models

Global relaxation model

Glassy
1.E+09
PS DOW @ 200°C G*HF(ω)
GEX MWD
1.E+08 Rubber
1.E+07 G*A(ω)
1.E+06

1.E+05 Rubber
G*[Pa]

1.E+04
Experimantal data
Experimantal data G*B(ω)
Complete Model
1.E+03 Complete Model
Process C
1.E+02 Process C
Process A Reptation :
1.E+01 Process A
Process B
Process B
G*C(ω)
1.E+00
Process HF
Process HF
1.E-01
1.E-04 1.E-02 1.E+00 1.E+02 1.E+04 1.E+06 1.E+08 1.E+10 Addition of
ω [rad/s]
behaviors

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Rheology models : processing Visco-elastic materials

Cutting Sodering
Blowing
thermoforming
Modulus

Extrusion

Injection

G' G"

Temperature

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 Rheology models : Help to formulate

Science of formulation

Peel
Tack @ room
temperature
Improve ageing
Tack,
Set time

Adjust viscosity

G’’

G’

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QUESTIONS ?

Contact:
Fabrice Flores
tel : +33 3 44 75 79 95
email : fabrice.flores@bostik.com

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