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and

Polymer Characterization

Asst Prof Anongnat Somwangthanaroj

Anongnat.s@chula.ac.th 20 Sep 2010

http://pioneer.netserv.chula.ac.th/~sanongn1/course.html

Fundamentals:

Why Rheology ? Fundamental Rheology Concepts and Parameters Fundamental Rheometry Concepts Viscosity, Viscoelasticiy and the Storage Modulus The Linear Viscoelastic Region (LVR)

AGENDA

Why Rheology ? Fundamental Rheology Concepts and Parameters Fundamental Rheometry Concepts Viscosity, Viscoelasticiy and the Storage Modulus The Linear Viscoelastic Region (LVR)

A Rheological Paradox

BECAUSE

If a material is pumped, sprayed, extended, extruded, molded, coated, mixed, chewed, swallowed, rubbed, transported, stored, heated, cooled, aged RHEOLOGY is important .!!

AGENDA

Why Rheology ? Fundamental Rheology Concepts and Parameters Fundamental Rheometry Concepts Viscosity, Viscoelasticiy and the Storage Modulus The Linear Viscoelastic Region (LVR)

(everything flows )

Heraclito de Samos (500 A.C.)

Deborah Number

De = / texp

Judges 5:5

Definition of Rheology

Rheology is the science of ____?____ and ____?___ of matter under controlled testing conditions .

flow deformation

Definition of Rheology

Rheology is the science of deformation and flow of matter under controlled testing conditions .

Shear Deformation F = A

y

x(t)

y0

A

x

. = t

Rheology: The study of deformation and flow of matter at specified conditions. Range of material behavior

Solid Like

(Ideal Solid

---------------------

Liquid Like

Ideal Fluid)

Classical Extremes

1678: Robert Hooke develops his True Theory of Elasticity

The power of any spring is in the same proportion with the tension thereof. Hookes Law:

=G

or

(Stress = G x Strain)

1000

Non-Linear Region

100.0

G = f()

osc. stress (Pa)

100.0

G' (Pa)

10.00

1687: Isaac Newton addresses liquids and steady simple shearing flow in his Principia The resistance which arises from the lack of slipperiness of the parts of the liquid, other things being equal, is proportional to the velocity with which the parts of the liquid are separated from one another.

Newtons Law: =

where is the Coefficient of Viscosity

1.000E5

Non-Newtonian Region

1.000E5

= f()

10000

1000

(Pa.s)

100.0

10.00

0.1000

1.000 1.000

(Pa)

Classical Extremes Ideal Solid

STEEL Strong Structure Rigidity Deformation Retains/recovers form Stores Energy

(Purely Elastic R. Hooke, 1678) [Energy]

-- [External Force] --

Ideal Fluid

WATER Weak Structure Fluidity Flow Losses form Dissipates Energy

(Purely Viscous I. Newton, 1687)

[Energy + time]

Apparent Fluid

- viscoelastic materials -

Deformation rate dependent viscosity Yield Stress (plasticity) Elasticity Thixotropy Transient behaviour

AGENDA

Why Rheology ? Fundamental Rheology Concepts and Parameters Fundamental Rheometry Concepts Viscosity, Viscoelasticiy and the Storage Modulus The Linear Viscoelastic Region (LVR)

Viscometer: instrument that measures the viscosity of a

fluid over a limited shear rate range

Viscosity over a wide range of shear rates, and Viscoelasticity of fluids, semi-solids and solids

Frame of Reference Recognize that a rheometer is a highly sensitive device used to quantify viscoelastic properties of the molecular structure of materials. A rheometer can not always mimic the conditions of a process, application or use. Rheometers determine apparent properties under a wide range of testing conditions.

The apparent behavior can be used as a finger print or benchmark of the material.

Constitutive Relations

Stress = Viscosity Shear rate

Concentric Cylinders Cone and Plate Parallel Plates Rectangular Torsion

Decane

Water

Steel

Why Rheology ? Fundamental Rheology Concepts and Parameters Fundamental Rheometry Concepts Viscosity, Viscoelasticiy and the Storage Modulus The Linear Viscoelastic Region (LVR)

Dynamic Testing

Deformation

An oscillatory (sinusoidal) deformation (stress or strain) is applied to a sample. The material response (strain or stress) is measured. The phase angle , or phase shift, between the deformation and response is measured.

Response

Phase angle

0 < < 90

Strain

Viscoelastic Parameters

The Complex Modulus: Measure of materials overall resistance to deformation. The Elastic (Storage) Modulus: Measure of elasticity of material. The ability of the material to store energy. The Viscous (loss) Modulus: The ability of the material to dissipate energy. Energy lost as heat. Tan Delta: Measure of material damping - such as vibration or sound damping.

Tan = G"/G'

Stress or Strain

Deformation

Time

USES Time dependent Thixotropy Cure Studies Stability against thermal degradation Solvent evaporation/drying

Why Rheology ? Fundamental Rheology Concepts and Parameters Fundamental Rheometry Concepts Viscosity, Viscoelasticiy and the Storage Modulus The Linear Viscoelastic Region (LVR)

Stress or Strain

Deformation

Time

The material response to increasing deformation amplitude (stress or strain) is monitored at a constant frequency and temperature.

USES Identify Linear Viscoelastic Region Strength of dispersion structure - settling stability Resilience

1000

Non-Linear Region

100.0

G = f()

10.00

Critical Strain c

1.0000 10.000 % strain 100.00 0.01000 1000.0

100.0

G' (Pa)

Frequency Sweep

Stress or Strain

Deformation

Time

The material response to increasing frequency (rate of deformation) is monitored at a constant amplitude (stress or strain) and temperature.

USES Viscosity Information - Zero Shear , shear thinning Elasticity (reversible deformation) in materials MW & MWD differences Polymer Melts and Polymer solutions. Finding Yield in gelled dispersions High and Low Rate (short and long time) modulus properties. Extend time or frequency range with TTS

Structural Recovery after Preshear

100.0

80.00

G' (Pa)

60.00

40.00

20.00

0 0

25.00

50.00

75.00

100.0

125.0

150.0

175.0

200.0

225.0

time (s)

1000

Non-Linear Region

100.0

G = f()

10.00

Critical Strain c

1.0000 10.000 % strain 100.00 0.01000 1000.0

100.0

G' (Pa)

Polyacrylamide Solution 20 C

1000 100.0 10.00 1.000 0.1000 0.01000 1.000E-3 1.000E-4 0.01000

TA Instruments

100.0 1000 100.0

4 Element Maxwell Fit

10.00

G' (Pa)

Straight Line Fit to Terminal Region of Data

0.1000 1.000 10.00 ang. frequency (rad/sec) 100.0

n' (Pa.s)

G'' (Pa)

G'

Situation

Sedimentation of fine powders in liquids

Shear Rate Range 10-6 to 10-3 10-2 to 10-1 10-1 to 101 100 to 102 101 to 102 101 to 102 101 to 103 100 to 103 103 to 104 104 to 105 104 to 106 105 to 106 103 to 107

Examples

Medicines, Paints, Salad Dressing

Leveling due to surface tension Draining off surfaces under gravity Extruders Chewing and Swallowing Dip coating Mixing and stirring Pipe Flow Brushing Rubbing High-speed coating Spraying Lubrication

Paints, Printing inks Toilet bleaches, paints, coatings Polymers, foods Foods Confectionery, paints Liquids manufacturing Pumping liquids, blood flow Painting Skin creams, lotions Paper manufacture Atomization, spray drying Bearings, engines

Strain

0

time

Hookean Solid Newtonian Fluid

Stress

Stress

0

time

time

Response of

Stress decreases with time starting at some high value and decreasing to zero.

Stress

0

Material

time

For small deformations (strains within the linear region) the ratio of stress to strain is a function of time only. This function is a material property known as the STRESS RELAXATION MODULUS, G(t) G(t) = s(t)/

Stress

Stain for t>t1 is constant Strain for t >t2 is 0

Strain

Strain

Stain rate for t>t1 is constant Strain for t>t1 increase with time Strain rate for t >t2 is 0

t1

time t2

t1 time t2

Creep t1> 0 Recovery t 2= 0 (after steady state)

/

Strain

Recoverable Strain

t2

time

Strain rate decreases with time in the creep zone, until finally reaching a steady state.

In the recovery zone, the viscoelastic fluid recoils, eventually reaching a equilibrium at some small total strain relative to the strain at unloading.

Reference: Mark, J., et.al., Physical Properties of Polymers ,American Chemical Society, 1984, p. 102.

1000000

HDPE

100000

viscosity (Pa.s)

LLDPE

10000

LDPE

1000 1.000E-4 1.00E-3 0.01000 0.1000 1.000 10.00

100000

viscosity (Pa.s)

10000

. () = ()

PDMS.05F-Flow step PDMS.08F-Flow step

1000

Dynamic data gives high shear rates unattainable in flow

100.0 1.000E-5

1.000E-3

10.00

1000

Glassy Region Transition Region

Terminal Region

Temperature

Glassy Region Transition Region Rubbery Plateau Region

Low MW

High Med. MW MW

Temperature

Heating Rate After Quench Cooling

Tg melt

1.000E10 0.4000 0.3500

1.000E10

G

1.000E9 0.3000

- transition Tg = 88.0C

1.000E9

0.2500 tan(delta)

G' (Pa)

Cold Crystallization

G'' (Pa)

1.000E8

0.2000

1.000E8

0.1500

1.000E7

0.1000

- transition -56.62C

1.000E7

0.05000

tan

-150.0 -100.0 -50.0 0 50.0 100.0 150.0 200.0 1.000E6 250.0

1.000E6 0 -200.0

temperature (Deg C)

1.000E10 2.250

G

2.000 1.000E9 1.750

1.000E10

Melt Tm = 240C

1.000E9

1.000E8

1.500

G

tan(delta)

1.000E8

G'' (Pa)

1.000E7

1.000E6

0.7500

1.000E6

tan

- transition Tg = 103C

1.000E5

10000 0 -200.0

-150.0

-100.0

-50.0

50.0

100.0

150.0

200.0

10000 250.0

temperature (Deg C)

1.000E10

1.000E9

G' (Pa) 1.000E8

1.000E7

1.000E6 -150.0 -100.0 -50.0 0 50.0 temperature (Deg C) 100.0

Cold Crystallization

150.0

200.0

250.0

Oxidation or Decomposition

Heat Flow

Temperature

BECAUSE

Thermal Analysis describes thermal transitions

Physical Properties of Structure Strength or weakness of the Structure

and because

Rheology

Shear Flexure

Tension

Compression

Creep

Creep

Stress relaxation

Creep

Stress relaxation

Creep

Stress relaxation

Acknowledgements

Abel Gaspar-Rosas, Ph.D.

TA Instruments Waters, Inc For graphs and figures

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